BACKGROUND As is generally known in prior art, chelating phosphine compounds when bound to metal atoms are useful as catalysts. To facilitate separation of the catalysts from a chemical process, phosphorus ligands have been attached to solid supports such as polymers ("Supported Metal Complexes", D. Reidel Publishing, 1985; Acta. Polymer. Hartley, F. R (Ed), 1987, vol. 4, pp. 1163-1225; Neckers, J. Macromol. Sci., Chem. 1987, A24, 431-48). Interest in using the combinatorial"split and mix synthesis"approach to generate polymer-bound ligands which could be tested as catalysts has brought to fore the importance of new chemistry with which to attach phosphine ligands to polymer supports (Balkenhohl et al., Angew. Chem., Int. Ed. Engl. 1996,35, 2288-2337; Gilbertson et al., J Organometallics 1996,15,4678-4680; Gilbertson et al., J. Am. Chem. Soc. 1994,116,4481-4482).

Novel processes have been discovered to prepare new compositions of matter that contain chelating phosphine compounds, including compounds of asymmetric diphosphines. Phosphine compounds have been shown to be useful when combined with transition metals as catalysts for chemical processes. The processes can also be utilized in a combinatorial scheme to produce libraries of phosphine compounds.

Addition of aldehyde in salicylaldehydes to acetylenes is known, but is unknown for addition to alkenes. (Kokai Tokkyo Koho JP 7853632; JP 76128205 Kokubo et al., J. Org. Chem. 1997,62,4564-4565.) The new phosphorus compounds have been shown to be useful as ligands in catalysts for the decarbonylation of the salicylaldehyde and insertion of the alkene, followed by ring closure forming a coumarin.

SUMMARY OF THE INVENTION This invention is directed to compositions and processes to prepare polymer supported phosphine and phosphine oxide compounds and the corresponding free compounds after their cleavage from the polymer support.

More specifically, the invention is directed to a process to prepare a supported phosphine compound selected from the group consisting of Formulae 1, 2,3,4,5,6, and 7 wherein: SS is a solid support; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; Rl, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQl, °Q2, PQ3Q4, and NQsQ6, where Ql, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, Rl and R3 together, or Ri and R2 together can optionally form a ring, the process comprising the steps of : a) contacting (i) a phosphine selected from the group consisting of XPRIR2, XR3P-A-PRIR2, HP (=O) RIR2, HP (=O) R3-A-PRIR2, and HP (=O) R3-A-P (=O) RIR2 wherein X is a halogen, with (ii) the solid support, resulting in at least one P in the phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and b) optionally replacing one or more substituent of the group RI, R2, or R3 with any other substituent of the group Rl, R2, or R3.

In all process and compositions embodiments of the invention, the preferred SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof.

The process is useful in producing the preferred supported phosphine compounds selected from the group consisting of Formulae 1 A, 2A, 3A, 4A, 5A, 6A, and 7A. wherein: Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More particularly, this process to prepare supported phosphine compounds uses the supported phosphine compound of Formula 1 A, where the process comprises the steps of : a) contacting (i) at least 2 molar equivalents of a phosphine of the Formula XR3P-A-PRIR2 wherein X is a halogen, with (ii) no more than one molar equivalent of Z, resulting in one P in the phosphine being covalently bonded to the Z, and b) optionally replacing one or more substitutent of the group Ri, R2, and R3 with any one or more of Rl, R2, and R3. In this process the SS is more preferably polystyrene; L is-CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally- substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, -(NR4)-, and-O-; R4(NR4)-, and-O-; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ 1, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Ri and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the process may use a supported phosphine compound of Formula 2A, with the process comprising the steps of : a) contacting (i) a phosphine of the Formula PRI R2X wherein X is a halogen, with (ii) the solid support, resulting in one P in the phosphine being covalently bonded to Z, and b) optionally replacing one or both of Rl and R2 with any other R1 or R2. In this process the SS is more preferably polystyrene; is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and Rj and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQI, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rj and R2 together with the P form a phosphole, aromatic or alkyl ring.

Alternatively, this process may use the supported phosphine compound of Formula 3A, with the process comprising the steps of :

a) contacting (i) no more than one molar equivalent of a phosphine of the Formula XR3P-A-PRIR2 wherein X is a halogen, with (ii) at least two molar equivalents of Z, resulting in both of the P in the phosphine being covalently bonded to the Z; and b) optionally replacing one or more of Rl and R2 with any one or more of R1 and R2. In this process the SS is more preferably polystyrene; L is- CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t- butyl; Ri and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQz, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Ri and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, this process may use the supported phosphine compound of Formula 4A, with the process comprising the steps of : a) contacting (i) a phosphine of the Formula HP (=O) R3-A-PRIR2 with (ii) the solid support, resulting in one P in the phosphine being covalently bonded to Z; and b) optionally replacing one or more of Rl, R2, and R3 with any one or more of Rl, R2, and R3. In this process the SS is more preferably polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQx, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rl and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, this process may use the supported phosphine compound of Formula 5A with the process comprising the steps of : a) contacting (i) a phosphine of the Formula HP (=O) R) R2 with (ii) a solid support of the formula

wherein the P in the solid support is covalently bonded to Z and Z'is selected from the group consisting of alkenyls, resulting in the P in the phosphine being covalently bonded to the P in the solid support via Z' ; and b) optionally replacing one or more of Rl, R2, and R3 with any one or more of Rl, R2, and R3. In this process the SS more preferably is polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t- butyl; and RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R, and R2 together with the P form a phosphole, aryl, or alkyl ring.

This invention is also directed to a process to prepare a combinatorial library of supported phosphine compounds selected from the group consisting of Formulae 1,2,3,4,5,6, and 7

wherein: SS is a solid support; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; Rl, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQsQ6, where Q1, Q2, Q3, Q4, Qs, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R, and R3 together, or Rj and R2 together can optionally form a ring, the process comprising the steps of : a) contacting (i) one or more phosphines selected from the group consisting of XPRIR2, XR3P-A-PRIR2, HP (=O) RIR2, HP (=O) R3-A-PRIR2, and HP (=O) R3-A-P (=O) RIR2 wherein X is a halogen, with (ii) one or more solid supports, resulting in at least one P in each phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and b) optionally replacing one or more RI, R2, or R3 with any other Rl, R2, or R3.

The process is useful in producing a combinatorial library in which the preferred supported phosphine compounds are selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

wherein: Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More preferably, this process to prepare a combinatorial library of supported phosphine compounds uses Formula 1A with the process comprising the steps of : a) contacting at least 2 molar equivalents of one or more phosphines of the Formula XR3P-A-PRIR2 wherein X is a halogen, with no more than one molar equivalent of one or more of Z, resulting in one P in each phosphine being covalently bonded to the Z; and b) optionally replacing one or more of Rl, R2, and R3 with any one or more of Rl, R2, and R3. In this process the SS more preferably is polystyrene; L

is-CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally- substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R, and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the process may use the supported phosphine compounds of Formula 2A with the process comprising the steps of : a) contacting one or more phosphines of the Formula PRIR2X wherein X is a halogen, with one or more solid supports, resulting in one P in each phosphine being covalently bonded to Z; and b) optionally replacing one or both of R, and R2 with any other Rl or R2. In this process the SS more preferably is polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and Rl and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where RI and R2 together with the P form a phosphole, aromatic, or alkyl ring.

Alternatively, the process may use the supported phosphine compounds of Formula 3A with the process comprising the steps of : a) contacting no more than one molar equivalent of one or more phosphines of the Formula XR3P-A-PRIR2 wherein X is a halogen, with at least two molar equivalents of one or more of Z, resulting in both of the P in each phosphine being covalently bonded to the Z; and b) optionally replacing one or more of Rl and R2 with any one or more of Rl and R2. In this process SS is more preferably polystyrene; L is- CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the

group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; Rl and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rj and R2 together with the P form a phosphole, aryl or alkyl ring.

Alternatively, the process may use the supported phosphine compounds of Formula 4A with the process comprising the steps of : a) contacting one or more phosphines of the Formula HP (=O) R3-A- PR1R2 with one or more solid supports, resulting in one P in each phosphine being covalently bonded to Z; and b) optionally replacing one or more of R, R2, and R3 with any one or more of Rl, R2, and R3. In this process the SS is more preferably polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and Ri, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Qi, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rl and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the process may use the supported phosphine compounds of Formula 5A with the process comprising the steps of : a) contacting one or more phosphines of the Formula HP (=O) RI R2 with one or more solid supports of the formula wherein the P in the solid support is covalently bonded to Z and Z'is selected from the group consisting of alkenyls, resulting in the phosphorus in each phosphine being covalently bonded to the phosphorus in the solid support via Z', and b) optionally replacing one or more of Ri, R2, and R3 with any one or more of Rl, R2, and R3. In this process the SS is more preferably polystyrene; L

is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t- butyl; and RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Ql Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where Rl and R2 together with the P form a phosphole, aryl, or alkyl ring.

Additionally, the invention is directed at a process to prepare a phosphine compounds of Formulae 8,9,10,11, and 12 wherein: A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and Rg are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4 and NQ5Q6, where QlQ2Q3eQ4 Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring; the process comprising the steps of : a) contacting (i) a supported phosphine selected from the group consisting of Formulae 1,2,3,4,5,6, and 7

wherein: SS is a solid support wherein at least one P in the phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometal groups; Rl, R2 and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQl, OQ, PQ3Q4, and NQ5Q6, where Ql, Q2, Q3, Q4, Qs, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, Rl and R3 together, or Rj and R2 together can optionally form a ring with (ii) a compound of the Formula ERg, wherein E is an electrophilic group and Rg is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQj, °Q2, PQ3Q4, and NQ5Q6, where Ql, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; thereby forming the corresponding compound of Formulae 1,2,3,4,5,6, and 7; and b) optionally replacing one or more substituent of the group R5, R6, R7, and R8 with any other substituent of the group R5, R6, R7, and R8.

More preferably, the process for preparing a phosphine compound uses a supported phosphine selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

wherein: Z is a divalent attaching group covalently attached to at least one P in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms; A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQl, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R5, R6, R7, and R8 can optionally together with any other of Rs, R6, R7, and R8

form a ring. Still more preferably in this process E is selected from the group consisting of hydrogen, PCl2, and SiMe3, and R5 is a halogen.

Also in this process, the supported phosphine compound is selected from the group consisting of Formulae 1 and 3, and the phosphine compound is of Formula 8. Also in this process at least one substitutent of the group R5, R6, R7, and R8 differs from the other substitutent of the group R5, R6, R7, and R8.

Also in this process, Z is preferably selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is preferably selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, R7, and R8 are preferably independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQl, OQ2, and PQ3Q4, where QIS Q2, Q3, and Q4 are preferably independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, R7, and R8 can optionally together with any other substituent of the group R5, R6, R7, and R8 form a ring.

Alternatively, the process may use the supported phosphine compound of Formula 2 and the phosphine compound of Formula 9. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQl, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, and R7 can optionally together with any other substituent of the group R5, R6, and R7 form a ring.

Alternatively, the process may use the supported phosphine compound of Formula 4 and the phosphine compound of Formula 10. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQs, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are

independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group Rs, R6, and R7 can optionally together with any other substituent of the group R5, R6, and R7 form a ring.

Alternatively, the process may use the supported phosphine compound selected from the group consisting of Formulae 3 and 5, and the phosphine compound of Formula 11. In this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, -(NR4)-, and-O-;(NR4)-, and-O-; A is selected from the group consisting of an optionally- substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R6, R7, and R8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R6, R7, and R8 can optionally together with any other substituent of the group R6, R7, and R8 form a ring.

Alternatively, the process may use the supported phosphine compound of Formula 2 and the phosphine compound of Formula 12. I this process more preferably Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Rs and R6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQs, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5 and R6 can optionally together with any other substituent of the group R5 and R6 form a ring.

This invention is still further directed to a process to prepare a combinatorial library of phosphine compounds selected from the group consisting of Formulae and 12

wherein: A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring; the process comprising the steps of : a) contacting (i) one or more supported phosphines selected from the group consisting of Formulae 1,2,3,4,5,6, and 7 wherein: SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; RI, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1 OQ2, PQ3Q4, and NQ5Q6, where Qi, Q2, Q3, Q4, Qs, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and

R2 and R3 together, Rj and R3 together, or R, and R2 together can optionally form a ring with (ii) one or more compounds of the Formula ERg, wherein E is an electrophilic group and Rg is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, Su 1, OQ, PQ3Q4, and NQ5Q6, where Ql, Q2, Q3, Q4, Qs, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; thereby forming the corresponding compounds of Formulae 1,2,3,4,5,6, and 7; and b) optionally replacing one or more substitutents of the group R5, R6, R7, and R8 with any other substitutent of the group R5, R6, R7, and Rg.

More particularly the process may use the supported phosphine compounds of the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

wherein: Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of

hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms; A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ i, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.

In this process preferably E is selected from the group consisting of hydrogen, PC12, and SiMe3, and Rs is a halogen. Additionally in this process preferably the supported phosphine compounds are selected from the group consisting of Formulae 1 and 3, and the phosphine compound is Formula 8. More preferaably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQl, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.

Alternatively in this process the preferred supported phosphine compounds are of Formula 2, and the phosphine compounds are of Formula 9. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, and R7, are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, and R7 can optionally together with any other of R5, R6, and R7 form a ring.

Alternatively in this process the preferred supported phosphine compounds are of Formula 4 and the phosphine compounds are of Formula 10. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, and R7 can optionally together with any other of R5, R6, and R7 form a ring.

Alternatively in this process the preferred supported phosphine compounds are selected from the group consisting of Formulae 3 and 5, and the phosphine compounds are of Formula 11. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, -(NR4)-, and-O-;(NR4)-, and-O-; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R6, R7, and R8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R6, R7, and R8 can optionally together with any other of R6, R7, and R8 form a ring.

Alternatively in this process the preferred supported phosphine compounds are of Formula 2, and the phosphine compounds are of Formula 12. More preferably in this process Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R5 and R6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ 1, OQ2, and PQ3Q4, where Q 1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5 and R6 can optionally together with any other of R5 and R6 form a ring.

This invention is still further directed to a supported phosphine compound selected from the group consisting of Formulae 1,2,3,4,5,6, and 7 wherein: SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; RI, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQ1, OQ2, PQ3Q4, andNQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R, and R3 together, or R1 and R2 together can optionally form a ring.

More preferably the supported phosphine compound is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

wherein: Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

Alternatively, the preferred supported phosphine compound is Formula 1A. More preferably in this supported phosphine compound the SS is polystyrene; L is-CH2- ; A is selected from the group consisting of an optionally- substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n- butyl, phenyl, and t-butyl; R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4,

where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the preferred supported phosphine compound is Formula 2A. More preferably in this supported phosphine compound the SS is polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n- butyl, phenyl, and t-butyl; and Ri and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aromatic, or alkyl ring.

Alternatively, the preferred supported phosphine compound is Formula 3A. More preferably in this supported phosphine compound the SS is polystyrene; L is-CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, - (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; RI and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the preferred supported phosphine compound is Formula 4A. More preferably in the supported phosphine compound of Claim 63 the SS is polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n- butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q 1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the preferred supported phosphine compound is Formula 5A. More preferably in this supported phosphine compound the SS is polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n- butyl, phenyl, and t-butyl; and R1, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring.

This invention is still further directed to a combinatorial library of supported phosphine compounds selected from the group consisting of Formulae 1,2,3,4,5,6, and 7 wherein: SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; RI, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl,

Br, I, SQ1, OQ2, PQ3Q4, andNQ5Q6, where Q1 Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or RI and R2 together can optionally form a ring.

Preferably the combinatorial library of this invention uses the supported phosphine compounds selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

wherein: Z is a divalent attaching group covalently attached to at least one phosphorus in each phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

Preferably, the combinatorial library uses the supported phosphine compounds of Formula 1A. More preferably in this combinatorial the SS is polystyrene; L is-CH2- ; A is selected from the group consisting of an optionally- substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R, and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 2A. More preferably in this combinatorial the SS is polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally- substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; and Ri and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQx, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rj and R2 together with the P form a phosphole, aromatic, or alkyl ring.

Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 3A. More preferably in this combinatorial library the SS is polystyrene; L is-CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally- substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, -(NR4)-, and-O-; R4(NR4)-, and-O-; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; RI and R2 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Ql, Q2, Q30, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rj and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 4A. More preferably in this combinatorial library the SS

is polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n- butyl, phenyl, and t-butyl; and Rl, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Ri and R2 together with the P form a phosphole, aryl, or alkyl ring.

Alternatively, the combinatorial library uses the supported phosphine compounds of Formula 5A. more preferably in this combinatorial library the SS is polystyrene; L is-CH2- ; Z is selected from the group consisting of optionally- substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n- butyl, phenyl, and t-butyl; and Rl, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQI, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where R, and R2 together with the P form a phosphole, aryl, or alkyl ring.

The invention is still further directed to a combinatorial library of phosphine compounds selected from the group consisting of Formulae 8,9,10, 11, and 12 wherein: A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Qi, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and

heterocycle; R5, R6, R7, and R8 are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQsQ6, where QlQ2nQ3sQ4sQ5 and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, R7, and R8 can optionally together with any other substituent of the group R5, R6, R7, and R8 form a ring.

Preferably in this combinatorial library of phosphine compounds A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQl, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 8. More preferably in this combinatorial library at least one of the substitutents of the group R5, R6, R7, and R8 differs from the other substituents of the group R5, R6, R7, and Rg.

Alternatively in this combinatorial library of phosphine compounds A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, R7, and R8 can optionally together with any other substituent of the group R5, R6, R7, and R8 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 9. More preferably in this combinatorial library A is an optionally- substituted carbon chain of 1-3 carbon atoms; R5, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, and R7 can optionally together with any other substituent of the group R5, R6, and R7 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 10. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; Rs, R6, and R7 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, and R7 can optionally together with any other substituent of the group R5, R6, and R7 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 11. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; R6, R7, and R8 are independently selected from the group consisting of Cl, alkyl, alkenyl, aryl, heterocycle, SQl, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R6, R7, and R8 can optionally together with any other substituent of the group R6, R7, and R8 form a ring.

Preferably in this combinatorial library the phosphine compounds are of Formula 12. More preferably in this combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5 and R6 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5 and R6 can optionally together with any other of R5 and R6 form a ring.

This invention is still further directed to a coordination compound comprising one or more transition metals complexed to a ligand selected from the group consisting of Formulae 1,2,3,4,5,6, and 7

wherein: SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometal groups; RI, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, Su 1, OQ2, PQ3Q4, and NQ5Q6, where Ql, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R, and R3 together, or Ri and R2 together can optionally form a ring.

Preferably the transition metal is selected from Periodic Group VIII.

Preferably the coordination compound is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

wherein: Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More preferably the coordination compound is Formula 1A. In this coordination compound still more preferably the SS is polystyrene; L is-CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, °Q2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from

the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rl and R2 together with the P form a phosphole, aryl or alkyl ring; and the transition metal is Rh.

Most preferably the coordination compound is polymer-bound 1- (1, 1-di-n- propylphosphino)-2-n-propylphosphinoethane and (1,5-cyclooctadiene)-rhodium (I) chloride dimer.

This invention is still further directed to a combinatorial library of coordination compounds comprising one or more transition metals complexed to one or more ligands selected from the group consisting of Formulae 1,2,3,4,5, 6, and 7 wherein: SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; Rl, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQl, °Q2 PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Qs, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, Rl and R3 together, or Rl and R2 together can optionally form a ring.

Preferably the transition metal is selected from Periodic Group VIII.

More preferably the combinatorial library is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A

wherein: Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More preferably the combinatorial library of coordination compounds is Formula 1A. In this combinatorial library of coordination compounds the SS is polystyrene; L is-CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the

group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, -(NR4)-, and-O-; R4(NR4)-, and-O-; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ 1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rl and R2 together with the P form a phosphole, aryl, or alkyl ring; and the transition metal is Rh.

This invention is still further directed to a combinatorial library of coordination compounds comprising one or more transition metals complexed to one or more ligands selected from the group consisting of Formulae 8,9,10,11, and 12 wherein: A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQl, OQ2, PQ3Q4, and NQ5Q6, where Ql, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of the substituents of the group R5, R6, R7, and R8 can optionally together with any other of the subsitutents of the group R5, R6, R7, and R8 form a ring.

More preferably in the combinatorial library A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring; and the transition metals are selected from Periodic Group VIII.

Still more preferably in the combinatorial library the ligands are of Formula 8. Still more preferably in the combinatorial library at least one substituent of the group R5, R6, R7, and R8 differs from the other substituents of the group R5, R6, R7, and Rg.

Alternatively, in this combinatorial library of coordination compounds A is an optionally-substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQl, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any substituent of the group R5, R6, R7, and R8 can optionally together with any other substituent of the group R5, R6, R7, and R8 form a ring; and the transition metal is Pd.

This invention is still further directed to a process to prepare coumarin comprising contacting salicylaldehyde with an acrylate of the formula wherein Riz is an alkyl group of 1-6 carbons. Preferably, the process to prepare coumarin is performed in the presence of a catalytic amount of a coordination compound comprising one or more transition metals complexed to a ligand selected from the group consisting of Formulae 1,2,3,4,5,6, and 7

wherein: SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; Rl, R2 and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQt, OQ2, PQ3Q4, andNQsQe, where Qi, Q, Qs, Q4, Q5.d Qg are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, Ri and R3 together, or R1 and R2 together can optionally form a ring.

Preferably, the process for pareparing coumarin uses a transition metal selected from Periodic Group VIII.

Preferably in the process to prepare coumarin, the ligand is Formula 1A: wherein: Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More preferably in the process to prepare coumarin, L is-CH2- ; A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl; RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl,

alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rl and R2 together with the P form a phosphole, aryl, or alkyl ring; and the transition metal is Rh.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides for a process to prepare novel, covalently attached phosphine ligands on polymer supports. These phosphine ligands are useful as catalysts when combined with a transition metal precursor. The present invention also allows synthesis of new free phosphine ligands by chemical cleavage from the solid support.

The invention provides for novel supported phosphine compositions of Formulae 1-7: wherein SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; Rl, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometallic, Cl, Br, I, SQl, °Q2, PQ3Q4, and NQsQ6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and

R2 and R3 together, Rj and R3 together, or Ri and R2 together can optionally form a ring.

By hydrocarbyl is meant a straight chain, branched or cyclic arrangement of carbon atoms connected by single, double, or triple carbon to carbon bonds and/or by ether linkages, and substituted accordingly with hydrogen atoms. Such hydrocarbyl groups may be aliphatic and/or aromatic. Examples of hydrocarbyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methyl- cyclohexyl, benzyl, phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, vinyl, allyl, butenyl, cyclohexenyl, cyclooctenyl, cyclooctadienyl, and butynyl. Examples of substituted hydrocarbyl groups include methoxy, phenoxy, toluyl, chlorobenzyl, fluoroethyl, p-CH3-S-C6H5,2-methoxy-propyl, and (CH3) 3SiCH2.

Virtually any solid material may be used as a support in the context of this invention as long as it meets the following criteria: The material is insoluble in organic, aqueous, or inorganic solvents.

Organic polymer supports are acceptable in this regard but they generally need to be crosslinked. Inorganic support, such as metal oxides (SiO2, A1203, TiO2, ZrO2, etc.), clays, and zeolites, and modified carbons are generally insoluble in these solvents and also may be used as supports.

The support contains reactive sites, which can be used for the covalent attachment of the phosphorus.

The reactive sites are isolated to prevent additional crosslinking during further chemical transformations.

The reactive sites are exposed to the reaction medium. With a polymer resin support this is achieved through the use of a resin which swells in a reaction solvent or is sufficiently porous to allow transport of the reaction medium through the polymer matrix.

The term"solid support"refers to a material having a rigid or semi-rigid surface that contains or can be derivatized to contain functionality, which covalently links a compound to the surface thereof. Other modifications may be made in order to achieve desired physical properties. Such materials are well known in the art and include, by way of example, polystyrene supports, polyacrylamide supports, polyethyleneglycol supports, metal oxides such as silica, and the like. Such supports will preferably take the form of small beads, pellets, disks, films, or other conventional forms, although other forms may be used.

A preferred solid support is an organic or inorganic polymer, to which the phosphorus can be covalently attached through a side chain or pendant group of the polymeric backbone. The polymer may be crosslinked or modified. Suitable preferred polymers useful in the preparation of a supported phosphine compound or a combinatorial library of supported phosphine compounds. include polyolefins, polyacrylates, polymethacrylates, and copolymers thereof that meet the general criteria described above. A more preferred polymeric support is polystyrene wherein the phosphorus is attached to a pendant phenyl group on the polystyrene backbone. Most preferred is polystyrene, crosslinked with divinylbenzene. Specifically, polystyrenes commonly used for solid phase synthesis have been used. These particular resins are crosslinked with from 1 to 10 wt % divinylbenzene. The styrene moieties are substituted in the para or meta positions. Only a portion of the styrene moieties are substituted, typically resulting in functional group loadings of approximately 0.2 to 2.0 mmole per gram of resin, although this value may be higher or lower.

Preferred embodiments for the novel supported phosphine compositions and for combinatorial libraries of supported phosphine compounds are selected from the group of Formulae 1A-7A:

where Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

Preferred compounds include those where L is-CH2-. Also preferred are those where A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally- substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl and t-butyl; RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQI, OQ2, and PQ3Q4, where Q1, Q2, Q3 and Q4 are selected from the group consisting of hydrogen, hydrocarbyl,

substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R, and R2 together with the P form a phosphole, aryl, or alkyl ring.

Most preferred compounds are those where the solid support is polystyrene (crosslinked with divinylbenzene) and where L= CH2 and Z, A, Ri, R2, and R3 are as shown in Tables 1-5 below.

TABLE1 FormulaIA Z A R1 R2 R3 N (t-butyl) (CH2) 2 chloro chloro chloro (CH2) 2 O chloro chloro chloro (CH2)5 (CH2)2 chloro chloro chloro N (t-butyl) (CH2) 2 4-methylphenyl 4-methylphenyl 4-methylphenyl N (t-butyl) (CH2) 2 4-chlorophenyl 4-chlorophenyl 4-chlorophenyl N (t-butyl) (CH2) 2 4-butylphenyl 4-butylphenyl 4-butylphenyl N (t-butyl) (CH2) 2 ethynyl ethynyl ethynyl N (t-butyl) (CH2) 2 propynyl propynyl propynyl N(t-butyl) (CH2) 2 4-fluorophenyl 4-fluorophenyl 4-fluorophenyl N (t-butyl) (CH2) 2 vinyl vinyl vinyl N (t-butyl) (CH2) 2 cyclopentyl cyclopentyl cyclopentyl N (t-butyl) (CH2) 2 decyl decyl decyl N (t-butyl) (CH2) 2 3,4-difluorophenyl 3,4-difluorophenyl 3, 4-difluorophenyl N (t-butyl) (CH2) 2 4-butylphenyl 4-butylphenyl 4-butylphenyl N (t-butyl) (CH2) 2 3-fluoromethyl-3-fluoromethyl-3-fluoromethyl- phenyl phenyl phenyl N (t-butyl) (CH2) 2 4-methylthiophenyl 4-methylthiophenyl 4-methyl- thiophenyl N (t-butyl) (CH2) 2 3-methoxyphenyl 3-methoxyphenyl 3-methoxy- phenyl N (t-butyl) (CH2) 2 3-fluoromethyl-3-fluoromethyl-3-fluoromethyl- phenyl phenyl phenyl N(t-butyl) (CH2) 2 4-methoxyphenyl 4-methoxyphenyl 4-methoxyphenyl N(t-butyl) (CH2) 2 mesityl mesityl mesityl N (t-butyl) (CH2) 2 2-phenylethyl 2-phenylethyl 2-phenyl- ethyl N (t-butyl) (CH2) 2 5-trifluoro-3,4,5-trifluoro- phenyl phenyl phenyl N (t-butyl) (CH2) 2 phenethyl phenethyl phenethyl N(t-butyl) (CH2) 2 o-tolyl o-tolyl o-tolyl Z A R1 R2 R3 N (t-butyl) (CH2) 2 3,5-difluorophenyl 3,5-difluorophenyl 3, 5-difluorophenyl N (t-butyl) (CH2) 2 2-thienyl 2-thienyl 2-thienyl N (t-butyl) (CH2) 2 2,3,4,5-tetramethyl- chloro phospholyl N (t-butyl) (CH2) 2 methyl methyl chloro N (t-butyl) (CH2) 2 6-trimethyl- phospholyl phenyl N (t-butyl) (CH2) 2 phenoxy phenoxy phenoxy (CH2) 5 (CH2) 2 methyl methyl methyl (CH2)5 (CH2) 2 ethyl ethyl ethyl (CH2) s (CH2) 2 n-propyl n-propyl n-propyl (CH2) 5 (CH2) 2 isopropyl isopropyl isopropyl (CH2) 5 (CH2) 2 butyl butyl butyl (CH2) 5 (CH2) 2 iso-butyl iso-butyl iso-butyl (CH2) 5 (CH2) 2 2-butyl 2-butyl 2-butyl (CH2) 5 (CH2) 2 cyclopentyl cyclopentyl cyclopentyl (CH2) 5 (CH2) 2 cyclohexyl cyclohexyl cyclohexyl (CH2) 5 (CH2) 2 dodecyl dodecyl dodecyl (CH2) 5 (CH2) 2 pentadecyl pentadecyl pentadecyl (CH2) 5 (CH2) 2 phenyl phenyl phenyl (CH2) 5 (CH2) 2 2-methyl-2-phenyl-2-methyl-2-phenyl-2-methyl-2-phenyl- propyl propyl propyl (CH2) 5 (CH2) 2 o-tolyl o-tolyl o-tolyl (CH2) 5 (CH2) 2 m-tolyl m-tolyl m-tolyl (CH2) 5 (CH2) 2 p-tolyl p-tolyl p-tolyl (CH2)5 (CH2)2 4-butylphenyl 4-butylphenyl 4-butylphenyl (CH2) 5 (CH2) 2 4-fluorophenyl 4-fluorophenyl 4-fluorophenyl (CH2) 5 (CH2) 2 3-bis (trimethyl-3-bis (trimethyl-3-bis (trimethyl- silyl) aminophenyl silyl) aminophenyl silyl) aminophenyl (CH2) 5 (CH2) 2 2,6-dimethylphenyl 2,6-dimethylphenyl 2, 6-dimethylphenyl (CH2) 5 (CH2) 2 3, 4-difluorophenyl 3,4-difluorophenyl 3,4-difluorophenyl (CH2) 5 (CH2) 2 3-fluoro-methyl-3-fluoro-methyl-3-fluoro-methyl- phenyl phenyl phenyl (CH2) 5 (CH2) 2 4-methylthiophenyl 4-methylthiophenyl 4-methylthiophenyl (CH2) 5 (CH2) 2 3-methoxyphenyl 3-methoxyphenyl 3-methoxyphenyl (CH2) 5 (CH2) 2 3-fluoromethyl-3-fluoromethyl-3-fluoro-methyl- phenyl phenyl phenyl Z A Rl R2 R3 (CH2) 5 (CH2) 2 2-methoxyphenyl 2-methoxyphenyl 2-methoxyphenyl (CH2) 5 (CH2) 2 4-methoxyphenyl 4-methoxyphenyl 4-methoxyphenyl (CH2) 5 (CH2) 2 4-phenoxyphenyl 4-phenoxyphenyl 4-phenoxyphenyl (CH2) 5 (CH2) 2 2, 4-difluorophenyl 2,4-difluorophenyl 2,4-difluorophenyl (CH2) (CH2) 2 2-naphthyl 2-naphthyl 2-naphthyl (CH2)5 (CH2)2 2-thiophenyl (CH2) 5 (CH2) 2 4-dimethylamino-4-dimethylamino-4-dimethylamino- phenyl phenyl phenyl N (t-butyl) C6H4 chloro chloro chloro N(t-butyl) C6H4 methylphenyl 4-methylphenyl 4-methylphenyl N (t-butyl) C6H4 chloro 3, 5-difluorophenyl 3,5-difluorophenyl (CH2) 5 (CH2) 2 chloro chloro cyclohexyl N(t-butyl) (CH2) 2 phenoxy phenoxy cyclohexyl N (t-butyl) (CH2) 2 n-propyl n-propyl n-propyl 0 (CH2) 2 chloro chloro chloro 0 (CH2) 2 i-propyl i-propyl i-propyl N (n-propyl) (CH2) 2 phenyl phenyl phenyl N (t-butyl) (CH2) 2 methyl phenyl phenyl N(n-propyl) (CH2) 2 2- (diphenylphos- phenyl phenyl phinyl) ethyl N (n-propyl) (CH2) 2 2- (methylphenyl- phenyl methyl phosphinyl)ethyl N (t-butyl) (CH2) 2 methyl methyl 3,5-difluorophenyl N (t-butyl) (CH2) 2 3, 5-difluorophenyl 3,5-difluorophenyl chloro TABLE 2 Formula 2A Z Rx R2 __ N(t-butyl) chloro chloro N (t-butyl) chloro phenyl N (t-butyl) vinyl phenyl N(t-butyl) phenyl phenyl N(t-butyl) mesityl phenyl N (t-butyl) ethyl phenyl N (t-butyl) allyl phenyl N(t-butyl) isopropyl phenyl Z Rl R2 N(t-butyl) vinyl vinyl N (t-butyl) mesityl mesityl N(t-butyl) isopropyl isopropyl N(n-propyl) chloro chloro N(n-propyl) chloro phenyl N (n-propyl) vinyl phenyl N(n-propyl) vinyl vinyl N(n-propyl) allyl phenyl N(n-propyl) allyl allyl N(ethyl) chloro phenyl N(chloro) chloro phenyl N(phenyl) chloro phenyl N(i-propyl) isopropyl phenyl N(phenyl) cyclohexyl cyclohexyl N(n-propyl) phenyl 2-methoxyphenyl N (n-propyl) phenyl 2,4-dimethoxyphenyl N(t-butyl) phenyl 2-methoxyphenyl N(n-propyl) phenyl 2-thiomethyphenyl N(n-propyl) phenyl 8- (dimethylamino) 1-naphthalenyl N(t-butyl) phenyl 2-thienyl N (n-propyl) phenyl 2-thiazole N(phenyl) phenyl 2-diethyl sulfide N(n-propyl) 2-furyl 2-thienyl N(n-propyl) 2-methylthiophenyl 2-methylthiophenyl N(n-propyl) 2-methoxyphenyl 2-methoxyphenyl N (n-propyl) 8-(dimethylamino) 1-naphthalenyl 8-(dimethylamino) 1-naphthalenyl N (phenyl) ethyl chloro N(phenyl) chloro chloro N(phenyl) isopropyl isopropyl N (n-propyl) phenyl 2-pyridyl N(n-propyl) H phenyl N (n-propyl) bromo furyl N(n-propyl) pyridyl pyridyl Z R1 R2 N (n-propyl) phenyl Me2N \/n e LvJ Me2N N(phenyl) ethyl Fe--j-f-) Me2N 1 JJ TABLE 3 Formula 3A

A R1 R2 N (n-propyl) (CH2) 2 chloro chloro N(n-propyl) (CH2) 2 n-butyl n-butyl N (n-propyl) (CH2) 2 t-butyl t-butyl N (n-propyl) (CH2) 2 n-heptyl N (n-propyl) (CH2) 2 2-methyl-2-phenylpropyl 2-methyl-2-phenylpropyl N (n-propyl) (CH2) 2 phenyl phenyl N(n-propyl) (CH2) 2 4-t-butylphenyl 4-t-butylphenyl N(n-propyl) (CH2) 2 mesityl mesityl N (n-propyl) (CH2) 2 IS, 2S-trans-1, 2-cyclohexanediol N(t-butyl) (CH2) 2 chloro chloro N (t-butyl) (CH2) 2 4-chlorophenyl 4-chlorophenyl N(t-butyl) (CH2) 2 phenethyl phenethyl N(t-butyl) (CH2) 2 i-propyl i-propyl N (t-butyl) (CH2) 2 phenoxy phenoxy N (cyclohexyl) (CH2) 2 chloro chloro N (cyclohexyl) (CH2) 2 n-heptyl N (n-propyl) (CH2) 2 n-heptyl n-heptyl TABLE 4 Formula 4A z A I Rl R2 R3 CH (OH) (CH2) 2 i-propyl i-propyl i-propyl

TABLE 5 Formula5A Z A R1 R2 R3 N (t-butyl) (CH2) 2 phenyl mesityl phenyl Another aspect of this invention is a combinatorial library of supported phosphine compounds selected from the group consisting of Formulae 1,2,3,4, 5,6, and 7 wherein SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; Rl, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ OQ2, PQ3Q4, and NQQg, where Q1, Q2, Q3, Q4, Qs, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, Ri and R3 together, or Rj and R2 together can optionally form a ring.

As used herein, a combinatorial library is an intentionally created collection of a plurality of differing molecules which can be prepared by selected synthetic means and screened for a desired activity or characteristic in a variety of formats (e. g., libraries of soluble molecules, libraries of compounds attached to resin beads, silica chips, or other solid supports). The libraries are generally prepared such that the compounds are in approximately equimolar quantities, and are prepared by combinatorial synthesis. Combinatorial synthesis refers to the parallel synthesis of diverse compounds by sequential additions of multiple choices of reagents which leads to the generation of large chemical libraries containing related molecules having molecular diversity. Screening methods for libraries vary greatly and are dependent upon a desired activity, the size of library, and the class of compounds in the library.

The libraries of the instant invention can be of any type. These types include but are not limited to arrays and mixtures. Arrays are libraries in which

the individual compounds are simultaneously synthesized in spatially segregated locations, typically identified by their location on a grid. Mixture libraries contain a mixture of compounds that are simultaneously synthesized and assayed.

Identification of the most active compound is then performed by any of several techniques well known in the combinatorial art, such as deconvolution.

A preferred solid support for the combinatorial libraries of the instant invention is an organic or inorganic polymer as described above, to which the phosphorus can be covalently attached through a side chain or pendant group of the polymeric backbone.

Preferred embodiments for the novel combinatorial libraries of phosphine compositions are shown in Formulae 1A-7A where Z is a divalent attaching group covalently attached to at least one phosphorus in each phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and -NR4-, where R4 is selected from the group consisting of an optionally- substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally- substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

Preferred compounds include those where L is-CH2-. Also preferred are those where A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms; Z is selected from the group consisting of an optionally- substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0- ; R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl and t-butyl; RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Qj, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where Rl and R2 together with the P form a phosphole, aryl, or alkyl ring.

Most preferred libraries are those where the solid support is polystyrene (crosslinked with divinylbenzene) and where L, Z, A, Ri, R2, and R3 are as shown in Tables 6-7 below.

TABLE 6 Formula 1A Mixed libraries L= CH2 Z= N (t-butyl) A= (CH2) 2 RI, R2, R3 n-propyl 3, 5-difluorophenyl L= CH2 Z= N (t-butyl) A= (CH2) 2 Ru, R2, R3 n-propyl cyclopentyl t-butyl phenyl 4-t-butylphenyl 2,4,6-trimethylphenyl 4-anisole 3-anisole 2-anisole 4-fluorophenyl 3,4-difluorophenyl 3,5-difluorophenyl L= CH2 Z= N (t-butyl) A= (CH2) 2 Ri) R2, R3 o-tolyl 2-thienyl 3,5-difluorophenyl

TABLE 7 Formula 1A Array library L=CH2, Z= (CH2) 5, A= (CH2) 2 Rl R2 R3 phenyl phenyl phenyl isopropyl isopropyl isopropyl butyl butyl butyl isobutyl isobutyl isobutyl 2-butyl 2-butyl 2-butyl cyclopentyl cyclopentyl cyclopentyl cyclohexyl cyclohexyl cyclohexyl dodecyl dodecyl dodecyl pentadecyl pentadecyl pentadecyl phenyl phenyl phenyl 2-methylphenylpropyl 2-methylphenylpropyl 2-methylphenylpropyl o-tolyl o-tolyl o-tolyl m-tolyl m-tolyl m-tolyl p-tolyl p-tolyl p-tolyl 4-butylphenyl 4-butylphenyl 4-butylphenyl 4-fluorophenyl 4-fluorophenyl 4-fluorophenyl 3-bis (trimethylsilyl) amino-3-bis (trimethylsilyl) amino-3-bis (trimethylsilyl) amino- phenyl phenyl phenyl 2,6-dimethylphenyl 2,6-dimethylphenyl 2,6-dimethylphenyl 3,4-difluorophenyl 3,4-difluorophenyl 3,4-difluorophenyl 3-fluoro-methylphenyl 3-fluoro-methylphenyl 3-fluoro-methylphenyl 4-methylthiophenyl 4-methylthiophenyl 4-methylthiophenyl 3-methoxyphenyl 3-methoxyphenyl 3-methoxyphenyl 3-fluoro-methylphenyl 3-fluoro-methylphenyl 3-fluoro-methylphenyl 2-methoxyphenyl 2-methoxyphenyl 2-methoxyphenyl 4-methoxyphenyl 4-methoxyphenyl 4-methoxyphenyl 4-phenoxyphenyl 4-phenoxyphenyl 4-phenoxyphenyl 2,4-difluorophenyl 2, 4-difluorophenyl 2, 4-difluorophenyl 2-naphthyl 2-naphthyl 2-naphthyl 2-thiophenyl 2-thiophenyl 2-thiophenyl 4-dimethylaminophenyl 4-dimethylaminophenyl 4-dimethylaminophenyl

Any reaction in which the phosphorus is covalently attached to the solid support may be used to prepare the compounds and libraries represented by Formula 1-7, such as those described in Encyclopedia of Inorganic Chemistry, John Wiley & Sons, Vol. 6, pg. 3149-3213, herein incorporated by reference.

One such scheme, another aspect of this invention, comprises the steps of contacting (i) a phosphine selected from the group consisting of XPRIR2, XR3P-A-PRIR2, HP (=O) RIR2, HP (=O) R3-A-PRIR2, and HP (=O) R3-A-P (=O) RIR2 wherein X is a halogen, with (ii) a solid support, resulting in at least one P in the phosphine attached indirectly or directly to the solid support via one or more covalent bonds, and optionally replacing one or more of RI, R2 or R3 with any other Rl, R2 or R3 defined above. To create a library, one or more phosphines are reacted with one or more solid supports, generating a plurality of supported phosphine compounds.

One embodiment of attaching the P to the solid support is via the reaction of the halogen or hydrogen bonded to the phosphorus in the phosphine with a nucleophilic group that is covalently attached to a solid support. The term nucleophilic group is a term well recognized in the art and refers to chemical moieties having a reactive pair of electrons. This scheme can easily be adapted for combinatorial synthesis.

When using diphosphines to prepare the compounds of the instant invention, the ratio of the reagents determines whether the product has one P in each phosphine or both P in each phosphine attached covalently to the solid support. When at least 2 molar equivalents of a phosphine of the Formula XR3P-A-PRIR2 is contacted with no more than one molar equivalent of the nucleophilic group attached to the solid support, the resulting product will have one P in the phosphine covalently bonded to the solid support. When no more than one molar equivalent of a phosphine of the Formula XR3P-A-PRIR2 is contacted with at least 2 molar equivalents of the nucleophilic group attached to the solid support, the resulting product will have both P in the phosphine covalently bonded to the solid support.

Other preferred processes of the instant invention to prepare a supported phosphine compound or a library of supported phosphine compounds include where: (1) the supported phosphine compound is of Formula 1A and the process comprises the steps of contacting at least 2 molar equivalents of a phosphine of the Formula XR3P-A-PRIR2 with no more than one molar equivalent of Z, resulting in one P in the phosphine being covalently bonded to the Z; (2) the supported phosphine compound is of Formula 2A and the process comprises the

steps of contacting a phosphine of the Formula PRIR2X with the solid support, resulting in one P in the phosphine being covalently bonded to Z; (3) the supported phosphine compound is of Formula 3A and the process comprises the steps of contacting no more than one molar equivalent of a phosphine of the Formula XR3P-A-PRIR2 with at least two molar equivalents of Z, resulting in both of the P in the phosphine being covalently bonded to the Z; (4) the supported phosphine compound is of Formula 4A and the process comprises the steps of contacting a phosphine of the Formula HP (=O) R3-A-PRI R2 with the solid support, resulting in one P in the phosphine being covalently bonded to Z, and (5) where the supported phosphine compound is of Formula 5A and the process comprises the steps of contacting a phosphine of the Formula HP (=O) RIR2 with a solid support of the formula wherein the P in the solid support is covalently bonded to Z and Z'is selected from the group consisting of alkenyls, resulting in the P in the phosphine being covalently bonded to the P in the solid support via Z'.

More preferred is where SS is polystyrene, L is-CH2-, Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms, -(NR4)-and-O-,(NR4)-and-O-, A is selected from the group consisting of an optionally- substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl, and RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQl, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle; and where RI and R2 together with the P form a phosphole, aryl, or alkyl ring.

Examples of reactions to prepare the compounds are shown but not limited to those in Scheme 1 below, where X is a halogen, M is any metal, R can be one or more of RI, R2, or R3, and RI, R2, R3, R4, Z, and A are as defined above. The Z, O, S, and N substituents are covalently attached to the solid support.

Scheme 1 Any of the substituents in the above compounds may be replaced by other functional groups using any procedure known in the art. One or all of the substituents can be reacted in a single reaction, depending on the choice of reactants and reaction conditions. These reactions can easily be adapted for combinatorial processes. Examples of suitable procedures are shown by but not limited to those depicted in Scheme 2 below, where X, M, and A are as defined above, and R indicates any of Rl, R2, or R3, as defined above. Examples of suitable definitions for M include Mg, Li, and Zn. Y is any linking group with the proper orientation or with enough flexibility to allow the reaction to proceed. The choice of Y will determine whether the ring is formed between two phosphorus atoms or on one phosphorus atom. Examples of suitable linking groups include hydrocarbylene, substituted hydrocarbylene, and organometallic compounds.

Scheme 2

The processes of the instant invention and of Schemes 1-2 are preferably performed under dry, inert atmosphere with dry, deoxygenated solvents. Any solvent is suitable provided that it is inert to all reagents and products. Optimum temperatures are about-80 to about 200 °C, preferably about-80 to about 150 °C.

The invention provides for novel phosphine compositions of Formulae 8-12: where A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ I I OQ2, PQ3Q4, and NQsQ6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.

Preferred embodiments for these phosphine compositions are where A is an optionally-substituted carbon chain of 1-3 carbon atoms ; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQl, OQ2, and PQ3Q4, where QloQ2nQ3 and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other R5, R6, R7, and R8 form a ring. More preferred embodiments for Formula 8 are where at least one of Rs, R6, R7, and R8 are different from the rest. Most preferred embodiments are shown in Tables 8-12 below.

TABLE 8 Formula 8 A = (CH2) 2 Rd ; R6 R7 R8 chloro 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl chloro phenoxy phenoxy phenoxy ethoxy phenyl phenyl phenyl ethoxy ethyl ethyl ethyl ethoxy isobutyl isobutyl isobutyl R5 R6 R7 R8 ethoxy 4-fluorophenyl 4-fluorophenyl 4-fluorophenyl methoxy 4-chlorophenyl 4-chlorophenyl 4-chlorophenyl methoxy mesityl mesityl mesityl methoxy phenethyl phenethyl phenethyl I-propylthio phenyl phenyl phenyl 1-propylthio isopropyl isopropyl isopropyl 1-propylthio 3,4,5-trifluorophenyl 5-trifluorophenyl diethylamino isopropyl isopropyl isopropyl chloro o-tolyl o-tolyl o-tolyl chloro 2-thienyl 2-thienyl 2-thienyl H 3,5-difluorophenyl 3,5-difluorophenyl 3, 5-difluorophenyl phenyl 3,5-difluorophenyl 3, 5-difluorophenyl 3, 5-difluorophenyl o-tolyl 3,5-difluorophenyl 3, 5-difluorophenyl 3, 5-difluorophenyl m-tolyl _ 3, 5-difluorophenyl 3, 5-difluorophenyl 3, 5-difluorophenyl p-tolyl 3,5-difluorophenyl 3, 5-difluorophenyl 3, 5-difluorophenyl 4- (t-butyl) phenyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl mesityl 3,5-difluorophenyl 3, 5-difluorophenyl 3, 5-difluorophenyl 2,5-dimethylphenyl 3,5-difluorophenyl 3, 5-difluorophenyl 3,5-difluorophenyl 3-methyl-4-fluoro-3, 5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl phenyl 3,4,5-trifluorophenyl 3, 5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl methyl 3,5-difluorophenyl 3, 5-difluorophenyl 3,5-difluorophenyl ethyl 3,5-difluorophenyl 3,5-difluorophenyl 3, 5-difluorophenyl n-propyl 3,5-difluorophenyl 3,5-difluorophenyl 3, 5-difluorophenyl cyclopentyl 3,5-difluorophenyl 3, 5-difluorophenyl 3,5-difluorophenyl n-heptyl 3,5-difluorophenyl 3, 5-difluorophenyl 3,5-difluorophenyl cyclohexyl 3,5-difluorophenyl 3, 5-difluorophenyl 3, 5-difluorophenyl phenylmethyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl 2-butyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl t-butyl 3,5-difluorophenyl 3, 5-difluorophenyl 3, 5-difluorophenyl n-pentadecyl 3,5-difluorophenyl 3, 5-difluorophenyl 3,5-difluorophenyl 3,5-phenyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl i-propyl 3,5-difluorophenyl 3,5-difluorophenyl 3, 5-difluorophenyl 3-chloro-4-fluoro-3, 5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl phenyl R5 R6 R7 R8 phenethyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl i-butyl 3,5-difluorophenyl 3,5-difluorophenyl 3, 5-difluorophenyl 2-methyl-2-phenyl-3, 5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl propyl n-decyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl 3,4-dimethoxyphenyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl 2-methoxy-4-fluoro-3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl phenyl 2-methoxy 3, 5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl 4-phenoxyphenyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl allyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl thiophenyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl phenoxy 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl H o-tolyl o-tolyl o-tolyl phenyl o-tolyl o-tolyl o-tolyl o-tolyl o-tolyl o-tolyl o-tolyl m-tolyl o-tolyl o-tolyl o-tolyl p-tolyl o-tolyl o-tolyl o-tolyl 4-(t-butyl) phenyl o-tolyl o-tolyl o-tolyl mesityl o-tolyl o-tolyl o-tolyl 2,5-dimethylphenyl o-tolyl o-tolyl o-tolyl 3-methyl-4-fluoro-o-tolyl o-tolyl o-tolyl phenyl 3,4,5-trifluorophenyl o-tolyl o-tolyl o-tolyl methyl o-tolyl o-tolyl o-tolyl ethyl o-tolyl o-tolyl o-tolyl n-propyl o-tolyl o-tolyl o-tolyl cyclopentyl o-tolyl o-tolyl o-tolyl n-heptyl o-tolyl o-tolyl o-tolyl cyclohexyl o-tolyl o-tolyl o-tolyl phenylmethyl o-tolyl o-tolyl o-tolyl 2-butyl o-tolyl o-tolyl o-tolyl t-butyl o-tolyl o-tolyl o-tolyl n-pentadecyl o-tolyl o-tolyl o-tolyl 3,5-phenyl o-tolyl o-tolyl o-tolyl R5 R6 R7 R8 i-propyl o-tolyl o-tolyl o-tolyl 3-chloro-4-fluoro-o-tolyl o-tolyl o-tolyl phenyl phenethyl o-tolyl o-tolyl o-tolyl i-butyl o-tolyl o-tolyl o-tolyl 2-methyl-2-phenyl-o-tolyl o-tolyl o-tolyl propyl n-decyl o-tolyl o-tolyl o-tolyl 3,4-dimethoxyphenyl o-tolyl o-tolyl o-tolyl 2-methoxy-4-fluoro-o-tolyl o-tolyl o-tolyl phenyl 2-methoxy o-tolyl o-tolyl o-tolyl 4-phenoxyphenyl o-tolyl o-tolyl o-tolyl allyl o-tolyl o-tolyl o-tolyl thiophenyl o-tolyl o-tolyl o-tolyl phenoxy o-tolyl o-tolyl o-tolyl H 2-thienyl 2-thienyl 2-thienyl phenyl 2-thienyl 2-thienyl 2-thienyl o-tolyl 2-thienyl 2-thienyl 2-thienyl m-tolyl 2-thienyl 2-thienyl 2-thienyl p-tolyl 2-thienyl 2-thienyl 2-thienyl 4- (t-butyl) phenyl 2-thienyl 2-thienyl 2-thienyl mesityl 2-thienyl 2-thienyl 2-thienyl 2,5-dimethylphenyl 2-thienyl 2-thienyl 2-thienyl 3-methyl-4-fluoro-2-thienyl 2-thienyl 2-thienyl phenyl 3,4,5-trifluorophenyl 2-thienyl 2-thienyl 2-thienyl methyl 2-thienyl 2-thienyl 2-thienyl ethyl 2-thienyl 2-thienyl 2-thienyl n-propyl 2-thienyl 2-thienyl 2-thienyl cyclopentyl 2-thienyl 2-thienyl 2-thienyl n-heptyl 2-thienyl 2-thienyl 2-thienyl cyclohexyl 2-thienyl 2-thienyl 2-thienyl phenylmethyl 2-thienyl 2-thienyl 2-thienyl 2-butyl 2-thienyl 2-thienyl 2-thienyl t-butyl 2-thienyl 2-thienyl 2-thienyl R5 R6 R7 R8 n-pentadecyl 2-thienyl 2-thienyl 2-thienyl 3,5-phenyl 2-thienyl 2-thienyl 2-thienyl i-propyl 2-thienyl 2-thienyl 2-thienyl 3-chloro-4-fluoro-2-thienyl 2-thienyl 2-thienyl phenyl phenethyl 2-thienyl 2-thienyl 2-thienyl i-butyl 2-thienyl 2-thienyl 2-thienyl 2-methyl-2-phenyl-2-thienyl 2-thienyl 2-thienyl propyl n-decyl 2-thienyl 2-thienyl 2-thienyl 3,4-dimethoxyphenyl 2-thienyl 2-thienyl 2-thienyl 2-methoxy-4-fluoro-2-thienyl 2-thienyl 2-thienyl phenyl 2-methoxy 2-thienyl 2-thienyl 2-thienyl 4-phenoxyphenyl 2-thienyl 2-thienyl 2-thienyl allyl 2-thienyl 2-thienyl 2-thienyl thiophenyl 2-thienyl 2-thienyl 2-thienyl phenoxy 2-thienyl 2-thienyl 2-thienyl chloro phenyl chloro phenyl phenyl chloro chloro phenyl chloro H chloro H H chloro chloro H chloro mesityl chloro mesityl mesityl chloro chloro mesityl methoxy 4-chlorophenyl methoxy 4-chlorophenyl 4-chlorophenyl methoxy methoxy 4-chlorophenyl n-heptyl methoxy n-heptyl methoxy methoxy n-heptyl n-heptyl methoxy chloro chloro 1S, 2S-trans-1, 2-cyclohexanediol chloro chloro n-heptyl phenyl phenoxy phenyl phenoxy phenoxy phenyl phenyl phenoxy 2-methyl-2-phenyl-3, 5-difluorophenoxy 2-methyl-2-phenyl-3, 5-difluorophenoxy propyl propyl 3,5-difluorophenoxy 2-methyl-2-phenyl-2-methyl-2-phenyl-3, 5-difluorophenoxy propyl propyl R5 R6 R7 R8 thiopropyl phenyl thiopropyl phenyl thiopropyl phenyl phenyl thiopropyl diethylamino chloro chloro chloro chloro phenyl phenyl phenyl ethoxy n-propyl n-propyl n-propyl ethoxy 3, 5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl ethoxy n-propyl 3,5-difluorophenyl 3,5-difluorophenyl ethoxy n-propyl n-propyl 3,5-difluorophenyl ethoxy 3, 5-difluorophenyl n-propyl n-propyl ethoxy 3,5-difluorophenyl n-propyl 3,5-difluorophenyl 3,5-difluorophenyl 3,5-difluorophenyl // TABLE 9 Formula 9 R7 R5 R6 chloro phenyl phenyl thiopropyl phenyl phenyl ethoxy i-propyl i-propyl i-propyl i-propyl i-propyl thiopropyl mesityl mesityl thiopropyl phenyl i-propyl chloro cyclohexyl cyclohexyl chloro vinyl phenyl chloro phenyl 2-methoxyphenyl chloro phenyl 2,4-dimethoxyphenyl chloro phenyl 2-methoxyphenyl chloro phenyl 2-thiomethyphenyl chloro phenyl 2-thienyl chloro phenyl 2-thiazole R7 R5 R6 chloro phenyl 2-diethyl sulfide chloro 2-methylthiophenyl 2-methylthiophenyl chloro 2-methoxyphenyl 2-methoxyphenyl TABLE 10 Formula 10

A = (CH2) 2 R7 R5 R6 methyl methyl methyl ethyl ethyl ethyl n-propyl n-propyl n-propyl i-propyl i-propyl i-propyl phenyl phenyl phenyl 3,5-difluorophenyl 3,5-difluorophenyl 3, 5-difluorophenyl mesityl mesityl mesityl phenyl phenyl methyl 2- (diphenylphosphinyl) ethyl phenyl phenyl 2-(methylphenylphosphinyl) ethyl phenyl methyl TABLE 11 Formula 11 A = (CH2)2

R6 R7 R8 phenyl phenyl H heptyl H phenyl phenyl mesityl phenethyl phenethyl H TABLE 12 Formula 12 R6 R5 i-propyl i-propyl mesityl phenyl i-propyl phenyl 2-thienyl 2-furyl 8-(dimethylamino) 1-naphthalenyl 8-(dimethylamino) 1-naphthalenyl R6 Rs phenyl 8-(dimethylamino) 1-naphthalenyl phenyl Fie-0 Me Me phenyl Fie-0 N M

The invention also provides for combinatorial libraries of the phosphine compositions of Formulae 8-12 where A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4 and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring. The libraries can be including arrays and any type of mixtures.

Preferred embodiments for these libraries are where A is an optionally- substituted carbon chain of 1-3 carbon atoms; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, ~ substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R 5, R 6 R 7, and R8 form a ring. More preferred embodiments for Formula 8 are where at least one of R 5, R 6 R 7, and R8 are different from the rest. Most preferred embodiments are shown in Tables 13-14 below.

TABLE 13 Formula 8 Array library A = (CH2) 2 _.-

R5 R6 R7 o-tolyl o-tolyl o-tolyl 2-thienyl 2-thienyl 2-thienyl 3,5-difluorophenyl 3, 5-difluorophenyl 3, 5-difluorophenyl Rus H phenyl o-tolyl m-tolyl p-tolyl 4- (t-butyl) phenyl mesityl 2,5-dimethylphenyl 3-methyl-4-fluorophenyl 3,4,5-trifluorophenyl methyl ethyl n-propyl cyclopentyl n-heptyl cyclohexyl phenylmethyl 2-butyl t-butyl n-pentadecyl 3,5-phenyl i-propyl 3-chloro-4-fluorophenyl phenethyl i-butyl 2-methyl-2-phenylpropyl R8 n-decyl 3,4-dimethoxyphenyl 2-methoxy-4-fluorophenyl 2-methoxy 4-phenoxyphenyl allyl thiophenyl phenoxy

TABLE 14 Formula 8 Mixed library A = (CH) R5 ethoxy R6, R7, R8 n-propyl 3,5-difluorophenyl Another aspect of this invention is a process to prepare the phosphine compound of Formulae 8-12 or a combinatorial library of phosphine compounds of Formulae 8-12 where A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups; R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQI, OQ2, PQ3Q4, and NQsQ6, where Ql, Q2, Q3 Q41 Qs, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring. The process comprises the steps of : (a) contacting (i) a supported phosphine selected from the group consisting of Formulae 5,6, and 7 where SS is a solid support wherein at least one P in the phosphine is attached indirectly or directly to the solid support via one or more covalent bonds; A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or

organometallic groups; RI, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where QIQ2fQ3Q4Q and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, Ri and R3 together, or Rj and R2 together can optionally form a ring; with (ii) a compound of the Formula ER9, wherein E is an electrophilic group and Rg is selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQsQ6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; thereby forming the corresponding compound of Formulae 1,2,3,4,5,6, and 7; and (b) optionally replacing one or more of R5, R6, R7, and R8 with any R5, R6, R7, and R8 To create a library, one or more supported phosphines are reacted with one or more compounds of the Formula ERg, generating a plurality of phosphine compounds.

A preferred process is where the phosphine or the library of phosphines produced by the above process is substituted asymmetrically; such compounds are difficult to prepare by techniques previously known in the art. The solid support serves essentially as a protecting group, facilitating the attachment of at least one substituent on a phosphorus that is different than the others. The process operates without any complicated separation or purification steps needed.

When the bisphosphine compounds of the present invention are unsymmetrically substituted, whether they are supported or unsupported, two isomers are present, cis and trans, as illustrated below.

The processes described herein prepare a 50/50 mixture of these two isomers. The isomers can be isolated by standard techniques such as recrystallization.

In the above process, E is any electrophilic group that will cleave the covalent bond attaching the phosphorus to the solid support. The term electrophilic group is a term well recognized in the art and refers to chemical

moieties, which can accept a pair of electrons from a nucleophilic group as defined above. Suitable electrophilic groups include-OH, trimethylsilyl, PC12, halogens, and protons donated from compounds such as acids, alcohols, or amines.

In the instance where ERs is water, the resulting POH group would rearrange to yield to form the compounds of Formula 10,11, or 12. These compounds can also be formed from any other of Formulae 8-12 via the replacement of one or more of R5, R6, R7, and R8 with an-OH group using any method known in the art. An equivalent rearrangement occurs when a PSH group is present.

Preferred processes for the preparation of the phosphine compounds or the library of phosphine compounds of the instant invention include those wherein the supported phosphine is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A where Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen; and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms; A is an optionally-substituted carbon chain of 1-3 carbon atoms; Rs, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1 Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle; and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.

Also preferred is where E is selected from the group consisting of hydrogen, PC12, and SiMe3, and where Rs is a halogen.

After cleavage from the solid support, R5, R6, R7, and R8 may be replaced with any other substituent using any method known in the art, in order to prepare a further range of compounds.

The process is preferably performed under dry, inert atmosphere with dry, deoxygenated solvents. Any solvent is suitable provided that it is inert to all reagents and products. Optimum temperatures are about-80 to about 200 °C, preferably about-80 to about 150 °C.

Preferred versions of the process to prepare the phosphine compounds or the library of phosphine compounds of the instant invention include those where

the supported phosphine compound is selected from the group consisting of Formulae 1 and 3 and the corresponding phosphine compound is of Formula 8, the supported phosphine compound is of Formula 2 and the corresponding phosphine compound is of Formula 9; the supported phosphine compound is of Formula 4 and the phosphine compound is of Formula 10, the supported phosphine compound is selected from the group consisting of Formulae 3 and 5 and the phosphine compound is of Formula 11, and the supported phosphine compound is of Formula 2, and the phosphine compound is of Formula 12. More preferred is where Z is selected from the group consisting of optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0-, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.

The phosphorus compounds and libraries described herein, both supported and unsupported, can be utilized as ligands for catalytic compounds.

Another aspect of the instant invention is a coordination compound comprising one or more transition metals complexed to a ligand selected from the group consisting of Formulae 1,2,3,4,5,6, and 7 where SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds, A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups, RI, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQl, OQ2, PQ3Q4, and NQsQ6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.

"Coordination compound"refers to a compound formed by the union of a metal ion (usually a transition metal) with a non-metallic ion or molecule called a ligand or complexing agent.

The transition metals are hereby defined as metals of atomic weight 21 through 83. Preferably, the transition metal is from Periodic Group VIII, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt. Preferred is Rh. The complex can be made by any synthetic method known in the art, either through direct reaction or via the use of a transition metal precursor. Many of these techniques are described in Hartley, ibid.

A preferred embodiment for the coordination compound is where SS is selected from the group consisting of polyolefins, polyacrylates, polymeth- acrylates, and copolymers thereof, and wherein the transition metals are selected from Periodic Group VIII.

Another preferred embodiment of the coordination compound is where the ligand is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A where Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydro- carbylene, substituted hydrocarbylene,-O-,-S-, and-NR4-where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen, and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More preferred is where the ligand is Formula 1A where SS is polystyrene, L is-CH2-, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, Z is selected from the group consisting of an optionally- substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0-, R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl and t-butyl, RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQI, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl or alkyl ring, and the transition metal is Rh. Most preferred is where the ligand is polymer-bound 1- (1, 1-di-n-propyl- phosphino)-2-n-propyl phospinioethane.

Most preferred is where the ligand is Formula 1A, L is (CH2), Z is N (t-butyl), A is (CH2) 2, Rlis n-propyl, R2 is n-propyl, R3 is n-propyl, and M is Rh.

Another aspect of the invention is a combinatorial library of coordination compounds comprising one or more transition metals complexed to one or more

ligands selected from the group consisting of Formulae 1,2,3,4,5,6, and 7 where SS is a solid support wherein at least one P in each phosphine is attached indirectly or directly to the solid support via one or more covalent bonds, A is a divalent group of 1-12 aliphatic or aromatic carbon atoms, linear or branched, optionally containing one or more heteroatoms or organometallic groups, R1, R2, and R3 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, OQ2, PQ3Q4, and NQ5Q6, where Q1, Q2, Q3, Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and R2 and R3 together, R1 and R3 together, or R1 and R2 together can optionally form a ring.

A preferred embodiment is where SS is selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, and copolymers thereof, and wherein the transition metals are selected from Periodic Group VIII.

Also preferred is where the ligand is selected from the group consisting of Formulae 1A, 2A, 3A, 4A, 5A, 6A, and 7A where Z is a divalent attaching group covalently attached to at least one phosphorus in the phosphine, selected from the group consisting of hydrocarbylene, substituted hydrocarbylene,-O-,-S-, and -NR4-, where R4 is selected from the group consisting of an optionally-substituted hydrocarbyl and halogen, and L is a divalent linking group covalently attached to Z and to SS, selected from the group consisting of optionally-substituted chains of from 1 to 12 linear, branched, and cyclic carbon atoms.

More preferred is where the ligand is Formula 1A, SS is polystyrene, L is -CH2-, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally-substituted carbon ring of 6-12 carbon atoms, Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms,- (NR4)-, and-0-, R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl, RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Q1, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where R1 and R2 together with the P form a phosphole, aryl, or alkyl ring, and the transition metal is Rh.

Another aspect of the instant invention are novel combinatorial libraries of coordination compounds comprising one or more transition metals complexed to one or more ligands selected from the group consisting of Formulae 8,9,10,11, and 12 where A is a divalent group of 1-12 aliphatic or aromatic carbon atoms,

linear or branched, optionally containing one or more heteroatoms or organo- metallic groups, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocycle, organometal, Cl, Br, I, SQ1, °Q2, PQ3Q4, and NQsQ6, where Q1SQ2>Q3Q4, Q5, and Q6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and any of Rs, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring.

Preferred is the combinatorial library where A is an optionally-substituted carbon chain of 1-3 carbon atoms, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Ql, Q2, Q3 and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydro- carbylamino, alkoxy, aryloxy, and heterocycle, and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring, and the transition metals are selected from Periodic Group VIII.

Also preferred is where the ligands are of Formula 8, and where at least one of R5, R6, R7, and R8 are different from the rest.

More preferred is where A is an optionally-substituted carbon chain of 1-3 carbon atoms, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, heterocycle, SQ1, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocycle, and any of R5, R6, R7, and R8 can optionally together with any other of R5, R6, R7, and R8 form a ring, and the transition metal is Pd.

Most preferred is where the ligand is of Formula 8, A = (CH2) 2, and where R5, R6, R7, Rg, and M are shown below: R5 R6 R7 R8 M thiopropyl phenyl thiopropyl phenyl Pd thiopropyl phenyl phenyl thiopropyl Pd The phosphine coordination compounds and libraries of phosphine coordination compounds can be prepared by any method known in the art, but preferably by those described herein.

Another aspect of the instant invention is a novel reaction to prepare coumarin, useful as an intermediate in pharmaceutical preparations, by contacting salicylaldehyde with an acrylate of the formula

Formula13 wherein Riz ils an alkyl group of 1-6 carbons. Preferred is where Rlo is n-butyl.

Salicyladehyde is converted via decarbonylation and insertion of an acrylate, followed by ring closure, as shown in Scheme 3.

Scheme 3 A preferred process is where the reaction is performed in the presence of a catalytic amount of the novel, phosphine coordination compounds of the instant invention, described above. Preferred is where the coordination compounds comprise a ligand selected from the group consisting of Formulae 1-7. Most preferred is where the metal is Rh, and the ligand is of Formula 1A where wherein SS is polystyrene, L is-CH2-, A is selected from the group consisting of an optionally-substituted carbon chain of 1-3 carbon atoms and an optionally- substituted carbon ring of 6-12 carbon atoms, Z is selected from the group consisting of an optionally-substituted carbon chain of 1-10 carbon atoms, -(NR4)-, and-O-, R4(NR4)-, and-O-, R4 is selected from the group consisting of chloro, cyclohexyl, n-propyl, i-propyl, n-butyl, phenyl, and t-butyl, RI, R2, and R3 are independently selected from the group consisting of hydrogen, Cl, alkyl, alkenyl, aryl, SQ1, OQ2, and PQ3Q4, where Ql, Q2, Q3, and Q4 are selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, and heterocycle, and where RI and R2 together with the P form a phosphole, aryl,

or alkyl ring. Most preferred is where SS is polystyrene, A is (CH2) 2, Z is N (t-butyl), and RI, R2, and R3 are n-propyl.

Any solvent is suitable for this process provided that it is inert to all reagents and products. Optimum temperatures are about-80 to about 200 °C, preferably about-80 to about 150 °C.

EXAMPLES The following non-limiting Examples are meant to illustrate the invention but are not intended to limit it in any way.

Materials and Methods All manipulations of air-sensitive materials were carried out with rigorous exclusion of oxygen and moisture in flame-dried Schlenk-type glassware on a dual manifold Schlenk line, interfaced to a high-vacuum (10-4-10-5 Torr) line, or in a nitrogen-filled Vacuum Atmospheres glovebox with a high-capacity recirculator (1-2 ppm of 02). Before use, all solvents were distilled under dry nitrogen over appropriate drying agents (such as sodium benzophenone ketyl and metal hydrides except for chlorinated solvents). Deuterium oxide, THF-Dg, C6D6 and chloroform-d were purchased from Cambridge Isotopes (Andover, MA). All organic and inorganic starting materials were purchased from Aldrich Chemical Co. (Milwaukee WI), Farchan Laboratories Inc. (Gainesville, FL), Strem Chemicals (Newburyport, MA), Calbiochem-NovaBiochem Corp. (San Diego, CA), Rieke Metals, Inc. (Lincoln, NE), or Lancaster Synthesis Inc. (Windham, NH), and when appropriate were distilled prior to use. The substrates zirconium metallacycles 2,3,4,5-tetramethylphospholylchloride, 2,3,4,5-tetraethyl- phospholyl-chloride, and 1,7-di-tert-butyl-l, 6-bicyclo [3,3] heptadiynyl- phospholylchloride were synthesized via modifications of literature methods (Fagan et al., J. Am. Chem. Soc. 1988,110, pp. 2310-2312).

Physical And Analvtical Measurements NMR spectra were recorded on either a Nicolet NMC-300 wide-bore (FT, 300 MHz, 1H; 75 MHz, 13c, 121 MHz 31p), or GE QM-300 narrow-bore (FT, 300 MHz, 1H) instrument. Chemical shifts (8) for IH, 13C are referenced to internal solvent resonances and reported relative to SiMe4.3 1 P NMR shifts are reported relative to external phosphoric acid. Analytical gas chromatography was performed on a Varian Model 3700 gas chromatograph with FID detectors and a Hewlett-Packard 3390A digital recorder/integrator using a 0.125 in. i. d. column with 3.8% w/w SE-30 liquid phase on Chromosorb W support. GC/MS studies were conducted on a VG 70-250 SE instrument with 70 eV electron impact ionization.

EXAMPLE 1 Reaction of Merrifield Resin with tert-Butylamine Merrifield Resin ResinI<BR> Merrifield Resin Resin I A solution of t-butylamine (70 g, 0.95 moles) and KI (0.3 g, 2 mmol) in 800 mL of THF was treated with Merrifield resin (chloromethylpolystyrene- divinylbenzene crosslinked with 2% divinylbenzene, 50 g, 0.89 mmol/g, 44.5 mmol) while stirring at room temperature for 30 min. The suspension was then refluxed for 48 h before the solution was filtered off. The resulting resin was washed sequentially with water (3 x 250 mL), THF (3 x 150 mL), hexane (3 x 200 mL). After drying in vacuo overnight, 51 g of the resin was obtained (98% yield according to N elemental analysis, anal. calculated for polymer-NHC (Me) 3: N, 1.25. Found: N, 1.22). The disappearance of l H resonances of polymer-Ph- CH2-Cl (6CH2= 5 ppm) and the appearance of I H resonances of polymer-Ph- CH2-NHC (Me) 3 (8CH2 =-3.7 ppm) indicates the complete transformation of the chloromethyl groups to tert-butylaminomethyl groups. Hereafter, this will be referred to as Resin I.

EXAMPLE 2 Reaction of tertiary-butylaminomethyl Merrifield Resin and 1,2-bis (dichlorophosphino) ethane

A solution of Cl2PCH2CH2PCl2 (15 g, 64.7 mmol) in 200 mL of THF was treated slowly with Resin I (15 g, 0.72 mmol/g, 10.8 mmol) while stirring at room temperature for a period of 30 min. before Et3N (5 g, 49 mmol) was added. The resulting suspension was stirred at room temperature overnight before the solution

was filtered off. The resin was sequentially washed with hexane (2 x 50 mL), CH2Cl2 (3 x 80 mL), and hexane (2 x 30 mL). The resulting resin was dried in vacuo overnight. 31P NMR (122 MHz, C6D6): 6 195,152 ppm. Hereafter this will be referred to as Resin II.

EXAMPLE 3 Reaction of 1,2-bis (dichlorophosphino) ethane with 1 % divinylbenzene crosslinked polystyrene containing 0.80 mmol/g of hydroxymethyl substitution.

A 500 mL round bottomed flask with a magnetic stirrer was charged with 10. 0 g of Cl2PCH2CH2PCl2 and 100 mL of tetrahydrofuran. In a 300 mL beaker was mixed 25 g of 1 % divinylbenzene cross-linked polystyrene with a loading of hydroxymethyl groups of 0.80 mmol/g (NovaBiochem 01-64-0110), 150 mL of tetrahydrofuran, and 3.00 g of 8.08 g of triethylamine. The mixture was added slowly to the flask containing the C12PCH2CH2PCl2 and was stirred for 4.0 h at room temperature. The resin was isolated by filtration, was washed once with 100 mL of tetrahydrofuran, five times with 100 mL of hexane, four times with 100 mL portions of dichloromethane, and twice with 100 mL portions of hexane.

The resin was then dried under high vacuum. 3 l p {l H} NMR (122 MHz, C6D6 solvent): 6 201 (broad singlet, 1 P), 194 (broad singlet, 1 P).

EXAMPLE 4 Reaction of Merrifield resin with 1,5-bis (bromomagnesium) pentane followed by reaction with 1,2-bis (dichlorophosphino) ethane

Resinni A two-necked 2 L round-bottomed flask with magnetic stirrer was charged with 500 mL (250 mmol) of BrMg (CH2) sMgBr (0.5 M in tetrahydrofuran) and 250 mL of tetrahydrofuran. To this was added while stirring 50 g (50 mmol) of Merrifield Resin (polystyrene 1% crosslinked with divinylbenzene, and 1.0 mmol/g of chloromethyl group substitution) in small portions over 30-40 minutes. The reaction mixture was stirred overnight at room temperature, and was then refluxed for 2 d. After cooling, the resin was isolated by filtration, was washed five times sequentially with 300 mL portions of tetrahydrofuran and 300 mL of hexane. This was then dried in vacuo. A one liter round-bottomed flask with a magnetic stirring bar was charged with 1,2-bis (dichlorophosphino)- ethane (46.4 g, 200 mmol) and tetrahydrofuran 500 mL. The resin was added to this solution, and the reaction mixture was stirred at room temperature overnight.

The resin was collected by filtration and was washed five times with 300 mL portions of tetrahydrofuran, and then five times with 300 mL of hexane. It was then dried in vacuo. Hereafter, this will be referred to as Resin III. 3 1 p I I H I NMR (122 MHz, C6D6 solvent): 8 107 (broad singlet); 197 (broad singlet). In some cases integration of these two resonances indicated the phosphorus reagent crosslinked some of the alkyl linking chains of the polymer to the degree of approximately 20%.

EXAMPLE 5 Reaction of Resin II with Grignard Reagents

To each of sixteen 20 mL glass vials was added 1.35 g of Resin II. To each of these vials was added the Grignard solution in the amount and concentration indicated in Table 2A below, and the volume in each vial was brought up to nearly the top of the vial by addition of tetrahydrofuran. The capped vials were agitated on an orbital shaker for 24 h, and each resin was collected by filtration. Each resin was washed twice with 10 mL of tetrahydrofuran, twice with 10% water/tetrahydrofuran, twice with 10 mL of tetrahydrofuran, and twice with 10 mL of hexane. The resins were then dried in vacuo and analyzed by 31P NMR (121 MHz, C6D6). Table 2A indicates the Grignard reagent and the molarity used, solvent, volume of reagent, yield, and NMR analysis of resulting products.

TABLE 2A YIELD Ex. Rg-MgX MOLARITY SOLVENT VOL. (mL) (g) 31p 5-A (4-methylphenyl) MgBr 1. 0 Ether 9 1. 42 46 5-B (4-chlorophenyl) MgBr 1. 0 Ether 9 1. 54 45 5-C (4-tert-butylphenyl) MgBr 2. 0 Ether 4. 5 1. 57 46 5-D (ethynyl) MgBr 0. 5 THF 18 1. 74 46 5-E (propynyl) MgBr 0. 5 THF 18 1. 33 46 5-F (4-fluorophenyl) MgBr 2. 0 Ether 4. 5 1. 52 45 5-G (vinyl) MgBr 1. 0 THF 9 1. 21 46 5-H (cyclopentyl) MgBr 2. 0 Ether 4. 5 1. 37 59 5-1 (decyl) MgBr 1. 0 Ether 9 1. 51 47 5-J (3,4-difluorophenyl) MgBr 0. 5 THF 18 1. 52 46 5-K(4-n-butylphenyl) MgBr 0. 5 THF 18 1. 51 46 5-L(3-fluoro-2-methylphenyl) MgBr 0. 5 THF 18 1. 63 37

YIELD Ex. R-M X MOLARITY SOLVENT VOL. (mL) (g) 31pg 5-M (4-methylthiophenyl) MgBr 0.5 THF 18 1. 53 46 5-N (3-methoxyphenyl) MgBr 0.5 THF 18 1.52 48 5-O (3-fluoro-4-methylphenyl) MgBr 0.5 THF 18 1.51 46 5-P (4-methoxyphenyl) MgBr 0.5 THF 18 1. 49 44 EXAMPLE 6 Reaction of Resin II with bis (cyclopentadienyl)-1,2,3,4-tetramethylbuta-1,4-dienylzirconi um (IV)

Resin IV Resin II (5 g) was reacted with 2.0 g of bis (cyclopentadienyl)-1,2,3,4- tetramethylbuta-1,4-dienylzirconium (IV) in anhydrous dichloromethane at room temperature. The resin was collected by filtration, was washed twice with 100 mL of hexane, and then three times with 100 mL of dichloromethane. It was then dried in vacuo. Hereafter, this will be referred to as Resin IV. 31 p {1H} NMR (122 MHz, CDC13 solvent): 8 14 (broad singlet); 160 (broad singlet).

EXAMPLE 7 Reaction of Resin II with bis (cyclopentadienyl)-dimethyl-1,4-dienylzirconium (IV)

A suspension of Resin II (0.9 g,-1.24 mmol/g, 1.1 mmol) in 100 mL of THF was treated with (P5-CsHs) 2ZrMe2 (0.70 g, 2.8 mmol) at room temperature for 8 h before the solution was filtered off. The resulting resin was washed with

THF (3 x 30 mL), CH2C12 (2 x 30 mL) and hexane (2 x 20 mL). The resin was dried in vacuo overnight. The polymer-supported 1.- (1, 1-dimethylphosphino)-2- chlorophosphinoethane, 0.9 g, was obtained. 31P NMR (122 MHz, C6D6): 8 155, -47 ppm.

EXAMPLE 8 Reaction of Resin IV with 2,4,6-trimethylphenylmagnesium bromide

Resin IV was reacted with an excess of 1.0 M solution of 2,4,6-trimethyl- phenylmagnesium bromide in ether. The resin was collected by filtration, and was washed twice with 100 mL portions of tetrahydrofuran, twice with 100 mL portions of hexane, twice with 150 mL portions of dichloromethane, once with 5% water/tetrahydrofuran, and finally twice with 100 mL portions of dichloro- methane. 3lP {lH} NMR (122 MHz, CDC13 solvent): b 17 (broad singlet); 49 (broad singlet).

EXAMPLE 9 Reaction of Resin III with Grignard Reagents

Thirty-two 20 mL glass vials were charged 1.0 g (1.0 mmol) of Resin III.

To each vial was added 9.0 mmol of a Grignard reagent as listed in the Table 3A below. The reactions were shaken overnight. Then the resin in each vial was collected by filtration, and washed with in order with the following solvents: tetrahydrofuran (2 x 10 mL), hexane (2 x 10 mL), 10% water/tetrahydrofuran (12 mL), tetrahydrofuran (2 x 10 mL), hexane (2 x 10 mL), tetrahydrofuran (2 x 10 mL), and hexane (2 x 10 mL). Each sample was then dried by flushing with nitrogen. The yield of each isolated resin was in the range 1.02-1. 110 g. All of

the resins had 3 IP NMR peaks in the range 50 to-50 ppm relative to external phosphoric acid which indicated the expected products. Table 3A indicates the Grignard reagent, molarity used, and volume of reagent.

Example 9-FF was prepared using the above procedure, except that (2-thiophenyl) Li was used in place of a Grignard reagent.

TABLE 3A Ex. Rg-MgX MOLARITY VOL. (mL) 9-A (methyl) MgBr 3 3 9-B (ethyl) MgBr 2 4.5 9-C (n-propyl) MgBr 2 4.5 9-D (isopropyl) MgBr 2 4.5 9-E (butyl) MgBr 2 4.5 9-F (iso-butyl) MgBr 2 4. 5 9-G (2-butyl) MgCI 2 4.5 9-H (cyclopentyl) MgBr 2 4.5 9-I (cyclohexyl) MgBr 2 4.5 9-J (dodecyl) MgBr 1 9 9-K (pentadecyl) MgBr 0. 5 18 9-L (phenyl) MgBr 3 3 9-M (2-methyl-2-phenylpropyl) MgCI 0. 5 18 9-N (ortho-tolyl) MgCI 9 9-O (meta-tolyl) MgCI 1 9 9-P (para-tolyl) MgBr 1 9 9-Q (4-tert-butylphenyl) MgBr 2 4.5 9-R (4-fluorophenyl) MgBr 2 4.5 9-S (3-bis (trimethylsilyl) aminophenyl) MgCI I 9 9-T (2,6-dimethylphenyl) MgBr 1 9 9-U (3,4-difluorophenyl) MgBr 0. 5 18 9-V (3-fluoro-2-methylphenyl) MgBr 0. 5 18 9-W (4-methylthiophenyl) MgBr 0. 5 18 9-X (3-methoxyphenyl) MgBr 0. 5 18 9-Y (3-fluoro-4-methylphenyl) MgBr 0. 5 18 9-Z (2-methoxyphenyl) MgBr 0. 5 18 77

Ex. Rg-MgX MOLARITY VOL. (mL) 9-AA (4-methoxyphenyl) MgBr 0. 5 18 9-BB (4-phenoxyphenyl) MgBr 0. 5 18 9-CC (2,4-difluorophenyl) MgBr 0. 5 18 9-DD (2-naphthyl) MgBr 0. 25 36 9-EE (4-dimethylaminophenyl) MgBr 0.5 18 9-FF (2-thiophenyl) Li 1 9 EXAMPLE 10 Reaction of Resin I with 1,2-bis (dichlorophosphino) benzene

Resn V Polymer-supported 1- (1, 1-dichlorophosphino)-2-chlorophosphinobenzene was prepared using the procedure for Resin II with 1,2-bis (dichlorophosphino)- benzene used in place of 1,2-bis (dichlorophosphino) ethane. 1,2-bis (dichloro- phosphino) benzene (12 g, 42.9 mmol) in 300 mL of THF was treated slowly with Resin I (10 g, 0.72 mmol/g, 7.2 mmol) and Et3N (4.4 g, 43.5 mmol). 31P NMR (122 MHz, C6D6): 6162, 124ppm. Hereafter this will be referred to as Resin V.

EXAMPLE 11 Reaction of Resin V with 4-methylphenylmagnesium bromide A suspension of Resin V (0.6 g,-0.72 mmol, 0.43 mmol) in 15 mL of THF was treated with 4-methylphenylmagnesium bromide (0.5 M solution in diethylether, 5.1 mmol) at room temperature for 5 min. The resulting mixture was stirred for 2 h before the solution was filtered off and the resin was washed with H20 (2 x 10 mL), CH2Cl2 (2 x 20 mL) and hexane (3 x 20 mL). After drying in vacuo, ca. 0.6 g of the polymer-bound 1- 1, 1-di (4-methylphenyl) phosphino-2- (4-methylphenyl) phosphinobenzene was obtained. 3 ! P NMR (122 MHz, C6D6): 6 43,-13 ppm.

EXAMPLE 12 Reaction of Resin II with 3,5-difluorophenylmagnesium bromide

A suspension of Resin II (2 g,-0.72 mmol/g, 1.44 mmol) in 100 mL of THF was treated with 3,5-difluorophenylmagnesium bromide (0.5 M in diethyl ether, 4.3 mmol) at room temperature for 8 h before the solution was filtered off.

The resulting resin was washed with THF (3 x 15 mL), CH2Cl2 (2 x 20 mL) and hexane (2 x 20 mL). The resin was dried in vacuo overnight. The polymer- supported 1- di (3,5-difluorophenyl) phosphino-2- (chlorophosphino) ethane, 2.0 g, was obtained. 31p NMR (122 MHz, C6D6): 8 155,-7.4 ppm.

EXAMPLE 13 Reaction of Resin I with mono-substituted 1,2-bis (dichlorophosphino) ethane

ResinVI A solution of Cl2PCH2CH2PCl2 (3.0 g, 12.6 mmol) in 200 mL of THF was treated slowly with cyclohexylzinc bromide (0.5 M in diethyl ether, 12.5 mmol) while stirring at 0 °C for a period of 30 min. before the resulting solution was warmed to room temperature and stirred overnight. The resulting mixture of cyclohexyl-substituted diphosphines were treated slowly with Resin I (2.0 g, 0.72 mmol/g, 1.44 mmol) for 10 min. before Et3N (0.73 g, 7.2 mmol) was added. The resulting suspension was stirred at room temperature overnight before the solution was filtered off. The resin was washed sequentially with hexane (2 x 30 mL), CH2Cl2 (3 x 30 mL), hexane (2 x 20 mL), and dried in vacuo overnight.

31p NMR (122 MHz, C6D6): 8 155,120 ppm. Hereafter this will be referred to as Resin VI.

EXAMPLE 14 Reaction of Resin II with Zr (OCH2CH2CH3) 4

A suspension of Resin II (10 g, 1.24 mmol/g, 12.4 mmol) in 250 mL of THF was treated slowly with Zr (OCH2CH2CH3) 4 (6.7 g, 20.5 mmol). The resulting mixture was stirred at room temperature for 4 h before the solution was filtered off and the resin was washed with THF (3 x 50 mL), H20 (2 x 10 mL), hexane (3 x 30 mL). The polymer-bound -P (OCH2CH2CH3) CH2CH2P (OCH2CH2CH3) 2 10 g, was obtained. 31p NMR (122 MHz, C6D6): 8 183,138 ppm.

EXAMPLE 15 Reaction of Chloromethylated Resin II with Lithium Phenoxide

A resin analogous to Resin II was prepared as follows. To 10 g of 2% divinylbenzene cross-linked chloromethylated polystyrene (1. 25 mmol of chloromethyl groups per gram) in 300 mL of tetrahydrofuran was added to a solution of tert-butylamine (14 g, 190 mmol). The reaction mixture was refluxed overnight and the resin was filtered, washed with H20 (200 mL), tetrahydrofuran (200 mL), hexane (200 mL), H20 (100 mL), and diethyl ether (200 mL). The resulting resin was dried in vacuo overnight. The resin was slowly added to a

solution of C12PCH2CH2PCl2 (7.4 g, 31.9 mmol) and Et3N (6.5 g, 64.2 mmol) in tetrahydrofuran (300 mL) at room temperature, and the resulting mixture was stirred overnight before filtration and washing with tetrahydrofuran (2 x 100 mL), hexane (2 x 100 mL), CH2Cl2 (2 x 100 mL), and hexane (2 x 100 mL). The resin was added to tetrahydrofuran (150 mL), and then at room temperature treated with a mixture of tetrahydrofuran (50 mL) and lithium phenoxide (62.0 mmol). After the mixture was stirred for 4 hr, the solvents were filtered off and the resulting resin was washed with tetrahydrofuran (3 x 100 mL), H20 (2 x 100 mL), and hexane (3 x 200 mL), dried in vacuo to give ca. 10 g of the title polymer-bound compound.

31p NMR (122 MHz, C6D6): 6 182,137.

EXAMPLE 16 Reaction of Resin VI with Lithium Phenoxide

A suspension of Resin VI (2 g,-0.72 mmol/g, 1.44 mmol) in 100 mL of THF was treated with PhOLi (1.0 M in diethyl ether, 7.2 mmol) at room temperature for 2 h before the solution was filtered off. The resulting resin was washed with H20 (5 mL), THF (2 x 20 mL) and hexane (2 x 20 mL). The resin was dried in vacuo overnight. 31p NMR (122 MHz, C6D6): 6 182,139 ppm.

COMBINATORIAL SYNTHESES EXAMPLE 17 Reaction of Resin II with a mixture of Grignard Reagents

A suspension of Resin II (1.0 g,-0.88 mmol/g, 0.88 mmol) in 15 mL of THF was treated slowly with a mixture of n-propylmagnesium bromide (2.0 M in

diethyl ether, 0.44 mmol) and 3,5-difluorophenylmagnesium bromide (0.5 M in diethyl ether, 0.44 mmol) over a period of 5 min. at room temperature. The resulting suspension was stirred at room temperature for 30 min. before the solution was filtered off and the resin was washed with THF (2 x 20 mL). The procedures above were successively repeated 4 times with the same amount of RMgBr mixture before the solution was filtered off and the resin was washed with H20 (2 x 3 mL), THF (2 x 10 mL) and hexane (2 x 15 mL). After drying in vacuo, a polymer-supported mixture of six components, 1.0 g, was obtained.

The resulting mixture resin with six components, and EtOH (0.28 g, 6.1 mmol) in 5 mL of THF was refluxed overnight. After cooling to room temperature, the resin was filtered off and washed with THF (2 x 5 mL). The combined filtrates were dried in vacuo. By 31 P-NMR and mass spectrum analysis it was shown that the mixture contained 6 compounds. 31P NMR (122 MHz, C6D6): 8 133.5,-27.4 ppm; 132.8,-16.6 ppm, ppm (cis-and trans- isomers); 132.1,-8.0 ppm; 119.3,-17.0 ppm, 119.1,-17.4 ppm (cis-and trans-isomers); 118.1,-8.5 ppm.

A polymer-supported mixture of 936 components (ligands) was produced according to the procedure above except that the resin was treated with a mixture of 12 RgMgX reagents (Rg = n-propyl, cyclopentyl, t-butyl, phenyl, 4-t-butyl- phenyl, 2,4,6-trimethylphenyl, 4-anisole, 3-anisole, 2-anisole, 4-fluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl) instead of 2 RgMgX reagents.

CLEAVAGE OF LIGANDS FROM THE RESIN EXAMPLE 18 Synthesis of 1- di (3,5-diflurophenyl) phosphino-2- (chloro-3,5- diflurophenylpho sphino) ethane

A suspension of Resin II (4.0 g,-0.96 mmol/g, 3.84 mmol) in 150 mL of THF was treated with 3,5-difluorophenylmagnesium bromide (0.5 M in diethyl ether, 38.4 mmol, 10 eq) at room temperature for 20 min, then the mixture was stirred overnight before the solution was filtered off. The resulting resin was washed with THF (2 x 50 mL), H20 (20 mL), THF (4 x 50 mL), and hexane (3 x 50 mL). The resin was dried in vacuo overnight. The polymer-supported

1- di (3,5-difluorophenyl) phosphino-2- chloro-3,5-diflurophenylphosphino)- ethane,-4.0 g, was obtained. 31P NMR (122 MHz, CDC13): 6 49.2,-7.3 ppm.

A suspension of the above resin (2.0 g, 0.96 mmol/g,-1.92 mmol,) in THF (100 mL) was treated dropwise with PC13 (2.64 g, 19.2 mmol) over 5 min. at room temperature. The resulting reaction mixture was then stirred overnight before the resin was filtered off and washed with THF (2 x 20 mL). Removal of solvents and excess PC13 in vacuo afforded 0.34 g (38%) of 1- di (3,5-difluoro- phenyl) phosphino-2- chloro-3,5-diflurophenylphosphino) ethane. 31 P NMR (202 MHz, CDC13): 90.8 (8, J = 29.8 Hz),-9.2 (6, J = 29.9 Hz). 1H NMR (500 MHz, CDC13): 7.03 (3H), 6.75 (6H), 2.02 (4H). 13C NMR (125.8 MHz, CDC13): 164.1,162.0,141.9,140.9,115.1,113.4,106.3,105.1,32.4,22.0.

HRMS Calcd for C2oHl3F6P2Cl: 464.0085. Found: 464.0075.

EXAMPLE 19 Synthesis of 1- (diphenylphosphinite)-2- (chlorophenylphosphinite) ethane Method A: A suspension of polymer-bound-P (PhO) CH2CH2P (OPh) 2 (from Example 15,0.5 g, 1.25 mmol/g,-0.62 mmol) in THF (20 mL) was treated dropwise with PCl3 (0.43 g, 3.1 mmol). The resulting reaction mixture was then stirred overnight before the resin was filtered off and washed with THF (10 mL).

The filtrate was dried in vacuo to remove the solvent and excess PC13, the residue was extracted with 3 x 20 mL of hexane. The combined hexane extracts were dried under reduced pressure to give 0.12 g (48 % yield) of (PhO) ClPCH2CH2P (OPh) 2.

31p NMR (122 MHz, C6D6): 6 199.5 (d, J = 16.8 Hz), 178.9 (d, J = 16.8 Hz) ppm.

Method B: A mixture of polymer-bound-P (PhO) CH2CH2P (OPh) 2 (from Example 15,0.5 g, 1.25 mmol/g,-0.62 mmol) and TMSCI (10 eq., 6.2 mmol) in THF (20 mL) was stirred at room temperature for 4 days before the resin was filtered off, the solvent and excess TMSCI were removed in vacuo. The phosphorus-31 NMR spectrum of the crude filtrate indicated the presence of the title compound (ca. 90%).

EXAMPLE 20 Synthesis of 1- (diphenylphosphino)-2- (ethoxylphenylphosphinite) ethane

A suspension of polymer-bound-P (Ph) CH2CH2P (Ph) 2 prepared as in Example 5 using phenyl magnesium bromide (13.6 g, 0.74 mmol/g, 1 mmol), and EtOH (5 g, 109 mmol) in THF (200 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 x 10 mL). The filtrate was dried in vacuo to remove the solvent and excess EtOH, the residue was extracted with 3 x 20 mL of hexane. The combined hexane extracts were dried under reduced pressure to give 2.17 g (59% yield) of (Ph) (EtO) PCH2CH2P (Ph) 2.3 ! p NMR (122 MHz, C6D6): 6 120.4,-11.6 ppm.

EXAMPLE 21 Preparation of Catalyst A flask was charged with 0.50 g of resin prepared as in Example 5 using n-propylmagnesium bromide and Resin II, 0.50 g (1,5-cyclooctadiene) rhodium (I) chloride dimer, and 20 mL of methylene chloride. This was allowed to stir at room temperature for 8 h. It was then filtered and the product was washed with hexane (2 x 15 mL), THF (2 x 10 mL), methylene chloride (2 x 10 mL), hexane (2 x 15 mL). To remove all excess (1,5-cyclooctadiene) rhodium (I) chloride dimer, the resin was then washed in portions with a total of 500 mL of methylene chloride until the washings were colorless. The resin was then dried in vacuo.

EXAMPLE 22 Reaction of Salicylalde and Butyl Acrylate to Form Coumarin

A flask was charged with 0.200 g of the complexed resin of Example 21, 1.00 g of salicylaldehyde, 2.00 g of butylacrylate, 0.122 g of sodium carbonate, and 5 mL of toluene. This was stirred at 100 °C for 48 h. The reaction mixture was filtered from the catalyst resin and then divided into two equal portions. The portions were each placed onto a 20 x 20 cm, 2000 micron thick silica gel preparatory chromatography plate, and each plate was eluted with 10% ethyl acetate/hexane solution.

On each of the plates, six bands were observed with the following Rf values: Band 1, Rf range 0.84-0.93; Band 2, Rf range 0.78-0.84; Band 3, Rf range 0.61-0.68; Band 4, Rf range 0.50-0.59; Band 5, Rf range 0.22-0.43; Band 6, Rf range 0.00-0.22. Each band was scraped off the plates, and the bands from each with similar Rf ranges were combined and extracted with 75 mL of ethylacetate.

Solvent was removed from these extracts in vacuo. The final weight from each band is as follows: Band 1,40 mg; Band 2,50 mg; Band 3,200 mg; Band 4, 90 mg; Band 5,200 mg; Band 6,110 mg. Proton NMR spectra and mass spectra were taken of each sample.

The product from Band 1 was identified as 2-hydroxybenzoic acid butyl ester with hydrocarbon impurities. The product from Band 2 was identified as essentially pure 2-hydroxybenzoic acid butyl ester. The product from Band 3 was identified as 3- (2-hydroxyphenyl)-2-methyl-3-oxo-propionic (-90 mol %). The product from Band 4 was identified as a mixture of 4- (2-hydroxyphenyl)-4-oxo butyric acid butyl ester and 2,2'-dihydroxybenzophenone in a 1.4: 1 mole ratio, respectively. The 4- (2-hydroxyphenyl)-4-oxo-butyric acid butyl ester was further purified by elution with 1: 1 methylene chloride: hexane on a preparatory silica gel chromatography plate. Two bands were partially separated. The bottom portion of the band was scraped off the plate and extracted with ethylacetate. Removal of solvent in vacuo yielded pure 4- (2-hydroxyphenyl)-4-oxo-butyric acid butyl ester.

The product from Band 5 was a mixture of coumarin and Z-3- (2-hydroxyphenyl)- acrylic acid butyl ester in a 1: 2 mole ratio, respectively. The products in Band 6 were a complex mixture of unidentified organic compounds. Based on the amount of starting salicylaldehyde, the following percent yields of each compound were obtained: 2-hydroxybenzoic acid butyl ester (3%), 3- (2- hydroxyphenyl)-2-methyl-3-oxo-propionic acid butyl ester (10%), 4- (2- hydroxyphenyl)-4-oxo butyric acid butyl ester (3%), 2,2'-dihydroxybenzophenone (2%), Z-3- (2-hydroxyphenyl)-acrylic acid butyl ester (8%), and coumarin (4%).

Polymer-Supported Synthesis of Diphosphine Monoxide Ligands Method A EXAMPLE 23 Synthesis of MePH (O) CH2CH2PMe2 A suspension of polymer-bound (Me) PCH2CH2P (Me) 2 (2.0 g, 1.0 mmol/g, 2.0 mmol, prepared using the procedure in Example 5 with methylMgBr) and H20 (0.60 g, 33.3 mmol) in THF (10 mL) was refluxed overnight, then the resin was filtered off and washed with THF (2 X 10 mL).

Removal of solvents and excess H20 from the filtrates by vacuum afforded _ 100 mg (33% yield) of MePH (O) CH2CH2PMe2. It was >95% pure by IH NMR and GC/MS. 31p NMR (121 MHz, CDC13, IH-decoupled): S 30.3 (d, JP P = 38.1 Hz),-44.5 (d, JP P = 38.1 Hz). 3 1 P NMR (121 MHz, CDC13, IH-coupled): 8 30.3 (d, Jp-H = 457.6 Hz),-44.5 (s). IH NMR (500 MHz, CDC13): 8 7.00 (d, Jp. = 457.6 Hz, 1H), 1.83 (m, 3H), 1.58-1.521 (m, 4H), 0.99 (m, 6H). 13C NMR (125 MHz, CDC13): S 25.4 (d, Jp. = 65.9 Hz), 21.8,13.1 (d, Jp-c = 65.7 Hz), 12.6.

HRMS: Calcd for CsHI4P2O (M+): 152.0520. Found: 152.0527.

EXAMPLE 24 Synthesis of EtPH (O) CH2CH2PEt2 A similar procedure to that described above was used to prepare EtPH (O) CH2CH2PEt2 using polymer-bound EtPCH2CH2PEt2 (2.0 g, 0.96 mmol/g, 1.92 mmol, prepared using the procedure in Example 5 with ethylMgBr) and H20 (0.6 g, 33.3 mmol). After the solvents were removed from the filtrates by vacuum, 160 mg (43% yield) of EtPH (O) CH2CH2PEt2 was obtained. It was >95% pure by IH NMR and GC/MS. 31p NMR (121 MHz, CDC13, tH-decoupled): b 36.2 (d, Jp-p = 36.0 Hz),-16.7 (d, JP P = 36.0 Hz). 31p NMR (121 MHz, CDC13, IH-coupled): 8 39.7 (d, Jp. H = 449.6 Hz),-16.6 (s). IH NMR (500 MHz, CDC13): 8 6.78 (d, Jp. H = 449.6 Hz, IH), 1.79 (m, 4H), 1.63 (m, 1H), 1.35 (m, 3H), 1.15 (m, 3H), 1.00 (m, 6H). 13C NMR (125 MHz, CDC13): 5 24.0 (d, Jp. = 62.8 Hz), 20.9 (d, Jp. = 65.7 Hz), 18.4,17.3,9.3,5.6. HRMS: Calcd for CgH2oP20 (M+): 194.0989. Found: 194.0952.

EXAMPLE 25 Synthesis of (CH3CH2CH2) PH (O) CH2CH2P (CH2CH2CH3) 2 A suspension of polymer-bound (CH3CH2CH2) PCH2CH2P (CH2CH2CH3) 2 (2.0 g, 0.92 mmol/g, 1.84 mmol, prepared using the procedure in Example 5 with n-propylMgBr) and H20 (0.6 g, 33.3 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess H20 from the filtrates by vacuum afforded 170 mg (39% yield) of the title compound.

It was >90% pure by I H NMR and GC/MS. 31p NMR (121 MHz, CDC13, I H-decoupled): 8 35.8 (d, Jp. p = 35.3 Hz),-26.3 (d, Jp. p = 35.3 Hz). 31p NMR (121 MHz, CDC13, lH-coupled): 8 35.8 (d, Jp. H = 448.6 Hz),-26.3 (s). I H NMR (500 MHz, CDC13): 8 6.83 (d, Jp. H = 448.0 Hz, 1H), 1.78 (m, 4H), 1.61 (m, 4H), 1.50 (m, 2H), 1.49-1.35 (m, 6H), 1.02 (t, J = 7.2 Hz, 3H), 0.94 (t, J = 7.10 Hz, 6H). 13C NMR (125 MHz, CDC13): 5 29.5 (d, Jp. = 65.5 Hz), 28.4,23.9 (d, Je. c = 62. 8 Hz), 18.3,17.5,15.0,14.8,14.4. HRMS: CalcdforCIlH26P2O (M+) : 236.1459. Found: 236.1428.

EXAMPLE 26 Synthesis of (Me2CH) PH (O) CH2CH2P (CHMe2) 2 An analogous procedure to that for (CH3CH2CH2) PH (O)- CH2CH2P (CH2CH2CH3) 2 was used for the synthesis of title compound using polymer-bound (Me2CH) PCH2CH2P (CHMe2) 2 (10. 0 g, 0.92 mmol/g, 9.2 mmol, prepared using the procedure in Example 5 with i-propylMgBr) and H20 (2.0 g, 111.1 mmol). After the solvents were removed from filtrates by vacuum, 912 mg

(42% yield) of (Me2CH) PH (O) CH2CH2P (CHMe2) 2 was obtained. It was >95% pure by I H NMR and GC/MS. 31p NMR (121 MHz, CDC13, IH-decoupled): 8 46.8 (d, JP P = 40.0 Hz), 10.5 (d, JP P = 40.4 Hz). 31p NMR (121 MHz, CDC13, IH-coupled): 8 46.8 (d, Jp-H = 442.3 Hz), 10.5 (s). IH NMR (500 MHz, CDC13): 8 6.55 (d, Jp-H = 442.3 Hz, 1H), 1.94-1.82 (m, 3H), 1.76-1.65 (m, 4H), 1.51 (m, 1H), 1.69-1.10 (m, 6H), 1.04-0.98 (m, 12H). 13C NMR (125 MHz, CDC13): 5 26.3 (d, Jp-c = 66.0 Hz), 24.0,23.0,18.5,14.7,12.8. HRMS: Calcd for CIlH26P2o (M+) : 236.1459. Found: 236.1448.

EXAMPLE 27 Synthesis of (Ph) PH (O) CH2CH2P (Ph) 2 A suspension of polymer-bound (Ph) PCH2CH2P (Ph) 2 (1. 5 g, 0.84 mmol/g, 1.26 mmol, prepared using the procedure in Example 5 with phenylMgBr) and H20 (0.5 g, 27.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess H20. The resulting residue was 200 mg (47% yield) of (Ph) PH (O) CH2CH2P (Ph) 2. It was >95% pure by I H NMR and GC/MS. 31p NMR (121 MHz, CDC13, IH-decoupled): 8 28.5 (d, J = 46. 0 Hz),-11.6 (d, J = 46. 0 Hz). 31P NMR (121 MHz, CDC13, iH-coupled): 8 28.5 (d, JP-H = 468.9 Hz),-11.6 (s). IH NMR (500 MHz, CDC13): 8 7.39 (d, Jp. n = 468.9 Hz, 1H), 7.51 (m, 2H), 7.43 (m, 1H), 7.35 (m, 2H), 7.24 (m, 4H), 7.19 (m, 6H), 2.16 (m, 2H), 1.95 (m, 2H). 13C NMR (125 MHz, CDC13) : 8 135. 4, 135. 3, 131. 2, 130. 9, 128. 4, 128. 3, 127. 4, 127. 0, 25. 0 (d, Jp c=65. 6Hz), 17.5. HRMS: Calcd for C20H20P2O(M+): 338.0989. Found: 338.0979.

EXAMPLE 28 Synthesis of (3,5-F2H3C6) PH (O) CH2CH2P (3,5-C6H3F2) 2 A suspension of polymer-bound (3,5-F2H3C6) PCH2CH2P (3,5-C6H3F2) 2 (1.0 g, 0.77 mmol/g, 0.77 mmol, prepared using the procedure in Example 5 with (3,5-difluorophenyl) MgBr) and H20 (0.60 g, 33.3 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess H20.

The resulting residue was 187 mg (54% yield) of (3,5-C6H3F2) PH (O) CH2CH2P (3,5-C6H3F2) 2. It was >95% pure by IH NMR and GC/MS. 31p NMR (121 MHz, CDC13, IH-decoupled): 8 24.1 (d, J = 47.3 Hz), -8.2 (d, J = 47.3 Hz). 31p NMR (121 MHz, CDCl3, IH-coupled): # 24.1 (d, Jp. n = 480.6 Hz),-8.2 (s). IH NMR (500 MHz, CDC13): 87.50 (d, Jp-H = 480. 6 Hz, 1H), 7.19-7.10 (m, 2H), 6.95 (m, 1H), 6.79 (m, 6H), 2.19-2.10 (m, 2H), 2.0-1.88

(m, 2H). 13C NMR (125 MHz, CDCl3) : 8 164. 4, 162. 1, 140. 3, 134. 0, 115. 1, 1 13. 0, 108. 6, 105. 4, 26. 0, 18. 8. HRMS : Calcd for C2oH24p2oF6 (M+) : 446.0424. Found: 446.0419.

EXAMPLE 29 Synthesis of (2,4,6-Me3H2C6) PH (O) CH2CH2P (2,4,6-Me3C6 H2) 2 A suspension of polymer-bound (2,4,6-Me3H2C6) PCH2CH2P (2,4,6- Me3H2C6) 2 (15.0 g, 0.76 mmol/g, 11.4 mmol, prepared using the procedure in Example 5 with (2,4,6-trimethylphenyl) MgBr) and H20 (6.5 g, 361 mmol) in THF (200 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 50 mL). The filtrate was dried in vacuo to remove the solvent and excess H20. The resulting residue was 2.53 g (48 % yield) of (2,4,6-Me3H2C6) PH (O) CH2CH2P (2,4,6-Me3H2C6) 2. It was >95% pure by IH NMR and GC/MS. 31P NMR (121 MHz, CDC13, IH-decoupled): 8 25.0 (d, J = 53.4 Hz),-18.1 (d, J = 53.4 Hz). 31P NMR (121 MHz, CDC13, IH-coupled): å 25.0 (d, JP-H = 470. 0 Hz),-18.1 (s). 31P NMR (121 MHz, C6D6, IH-coupled): 8 20.5 (d, Jp. H = 470. 0Hz),-18.0 (s). IH NMR (500 MHz, C6D6): 8 7.83 (d, Jp. H = 470.0 Hz, 1H), 6.59 (m, 4H), 6.48 (m, 2H), 2.63 (m, 4H), 2.24 (s, 6H), 2.21 (s, 12H), 2.02 (d, Jp. = 3.96 Hz), 1.93 (s, 3H). 13C NMR (125 MHz, C6D6): 8141.9,141.2,141.0,137.4,136. 9, 132. 4, 132. 2, 129. 8, 22. 7, 22. 5, 20. 4, 20. 3, 19.2,19.0. HRMS: Calcd for C29H38P2O(M+): 464.2398. Found: 464.2395.

EXAMPLE 30 A suspension of hydroxymethylpolystyrene-bound (i-C3H7) PCH2CH2P (i- C3H7) 2 (prepared using the procedure in Example 3, followed by reaction with (i-propyl) MgBr as in Example 5), 1.0 g, 0.68 mmol/g, 0.68 mmol) and H20 (0.4 g, 22.2 mmol) in 8 mL of THF was refluxed for 3h. The 3 lP NMR spectrum of this crude product indicated the presence of (Me2CH) PH (O) CH2CH2P (CHMe2) 2 (-70%). Removal of solvent and excess H20 afforded 40 mg (25% yield) of the title compound. 31P NMR (121 MHz, CDC13, IH-decoupled): 8 46.2 (d, JP P = 41.2 Hz), 9.1 (d, JP P = 38.2 Hz).

Method B EXAMPLE 31 A suspension of polymer-bound (C6H3F2) PCH2CH2P (C6H3F2) 2 (6.0 g, 0.77 mm/g, 4.6 mmol, prepared using the procedure in Example 5 with (3,5-difluorophenyl) MgBr) and PC13 (5.0 g, 36.4 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 5 mL) and hexane (2 X 10 mL). The combined filtrates were dried in vacuo to remove the solvent and excess PC13. The resulting residue was extracted with hexane (3 X 30 mL). The concentration of the extracts afforded 1.58 g (74%) of the title compound (C6H3F2) (Cl)PCH2CH2P (C6H3F2) 2. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDC13): 6 90.8 (d, J = 29.8 Hz),-9.2 (d, J = 29.9 Hz). 1H NMR (500 MHz, CDCl3): 8 7.03 (µ, 3H), 6.76 (, 6H), 2.02 (µ, 4H), 1.97.13C NMR (125 MHz, C6D6): â 164.1,162.0, 141.9,140.9,115.1,113.4,106.3,105.1,32.4,22.0. HRMS: Calcd for C2oHl3F6P2Cl: 464.0085. Found: 464.0075.

A solution of 50 mg (0.108 mmol) of (C6H3F2) (Cl) PCH2CH2P (C6H3F2) 2 and 0.04 g (2.2 mmol) of H20 in 10 mL of THF was refluxed overnight. After filtration, the solvent and excess H20 were removed in vacuo to give 38 mg (79%) of (C6H3F2) PH (O) CH2CH2P (C6H3F2) 2. It was >95% pure by IH NMR and GC/MS. 3 1 P NMR (121 MHz, CDC13, IH-decoupled): 8 24.1 (b, J = 47.3 Hz),-8. (8, J = 47.3 Hz). 31p NMR (121 MHz, CDCl3, IH-coupled): # 24.1 (d, Jp. H = 480.6 Hz),-8.2 (s). 1H NMR (500 MHz, CDCl3): 8 7.50 (â, Jp. n = 480.6 Hz, 1H), 7.19-7.10 (Il, 2H), 6.95 (j, 1H), 6.79 (µ, 6H), 2.19-2.10 (u, 2H), 2.0-1.88 (, 2H). 13C NMR (125 MHz, CDC13): 64.4,162.1,140.3,134.0,115.1, 113.0, 108. 6, 105. 4, 26. 0, 18. 8. HRMS : CalcdforC20H24P2OF6 (M+) : 446.0424. Found: 446.0419.

Method C EXAMPLE 32 A suspension of polymer-bound (CH3CH2CH2) PCH2CH2P (CH2CH2CH3) 2 (1.0 g, 0.92 mmol/g,-0.92 mmol, prepared using the procedure in Example 5 with (n-propyl) MgBr) and MeOH (0.1 g, 3.1 mmol) in THF (5 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrates were dried in vacuo to remove the solvent and excess MeOH. The residue was crude (CH3CH2CH2) P (OMe) CH2CH2P (CH2CH2CH3) 2. It was directly used for next reaction without further purification. 31P NMR (122 MHz, THF-D8): 8 138.5 (d, J = 19.8 Hz),-27.3 (d, J = 19.8 Hz). A solution of (CH3CH2CH2) P (OMe) CH2CH2P (CH2CH2CH3) 2 above and 0.1 g (5.6 mmol) of H20 in 1.0 mL of THF was stirred overnight at room temperature. The 3 1 P NMR spectrum of this crude product indicated the presence of (CH3CH2CH2) PH (O) CH2CH2P (CH2CH2CH3) 2 (~90%). Removal of solvent and excess H20 afforded 50 mg (23% yield) of the title compound. It was >90% pure by IH NMR and GC/MS. 31p NMR (121 MHz, THF-D8, IH-decoupled): 8 37.8 (d, Jp-p = 35.1 Hz),-27.0 (d, Jp-p = 35.1 Hz). 31P NMR (121 MHz, THF-D8, IH-coupled): 8 37.8 (d, Jp-h = 453.2 Hz),-27.0 (s).

IH NMR (500 MHz, CDC13): 8 6.83 (d, Jp-h = 448.0 Hz, 1H), 1.78 (m, 4H), 1.61 (m, 4H), 1.50 (m, 2H), 1.49-1.35 (m, 6H), 1.02 (t, J = 7.2 Hz, 3H), 0.94 (t, J = 7.10 Hz, 6H). 13C NMR (125 MHz, CDC13): 8 29.5 (d, Jp-c=65. 5Hz), 28.4, 23. 9 (d, Jp-c = 62. 8 Hz), 18. 3, 17. 5, 15. 0, 14. 8, 14. 4. HRMS : Calcd for C11H26P2O(M+): 236.1459. Found: 236.1428.

Solution Synthesis of Diphosphine Monoxide Ligands EXAMPLE 33 A solution of C12PCH2CH2PCl2 (1.0 g, 4.3 mmol) in 50 mL of THF was treated with a mixture of Et2NH (0.63 g, 8.6 mmol) in THF (5 mL) dropwise over a period of 10 min. at room temperature. The resulting solution was stirred for 2 h before removal of THF in vacuo. The residue was extracted with hexane (3 X 30 mL). Removal of the solvents from extracts gave a mixture of Et2NP (Cl) CH2CH2PCl2 [ca. 35% by 31p NMR, 31p NMR (121 MHz, CDC13, IH-decoupled): 8 193.4 (d, Jp-p = 19.8 Hz), 144.6 (â, Jp p = 18.4 Hz)], Et2NP (Cl) CH2CH2P (Cl) (NEt2) [ca. 15% by 31p NMR, 31p NMR (121 MHz, CDC13, IH-decoupled): 8 148.5 (s), 148.4 (s)], and unreacted C12PCH2CH2PCl2 (ca. 50% by 31P NMR, 31P NMR (121 MHz, CDC13, IH-decoupled): 8 191.4 (s)..

A solution of the mixture above was treated with PhMgCl (3 M solution in THF, 13 mmol) at room temperature over a period of 5 min., and the resulting solution was stirred for 30 min. before 1.0 mL of H20 was used to quench the reaction. After filtration, the solvents were removed in vacuo. The residue was extracted with hexane (3 X 30 mL). Extracts was dried at reduced pressure to give the compounds which were used directly for the next step without further purification.

A mixture of the compounds above and H20 (1.0 g, 55.5 mmol) in THF (10 mL) was refluxed overnight in a sealed reactor. After filtration, the filtrate was dried in vacuo to give 0.20 g of the residue. The 3 P NMR spectrum of this crude reaction mixture indicated the presence of PhPH (O) CH2CH2PPh2 (<5%), Ph2PCH2CH2PPh2 (ca. 80%) and two compounds (<5%) exhibiting two singlets at 8 27.5,27.3 ppm.

Synthesis of Polymer-Bound Bisphosphines Resin V EXAMPLE 34 A solution of n-propylamine (72 g, 1.22 moles) and KI (0.3 g, 2 mmol) in 800 mL of THF was treated with chloromethylpolystyrene-divinylbenzene (Merrifield resin, 2% DVB, 100 g, 0.72 mmol/g, 72 mmol) while stirring at room temperature for 30 min. The suspension was then refluxed for 24 h before the solution was filtered off. The resulting resin was washed with a mixture of H20/THF (20% H20,3 X 250 mL), THF (3 X 150 mL), hexane (3 X 200 mL).

After drying in vacuo overnight, 100 g of the resin were obtained. The disappearance of 1H resonances of polymer-Ph-CH2-Cl (CH2=-4. 5 ppm) and the appearance of 1H resonances of polymer-Ph-CH2-NHCH2CH2Me indicates the complete transformation of the chloromethyl groups to n-propylaminomethyl groups.

A solution of resin above (99.0 g, 0.709 mmol/g, 70.1 mmol) in 800 mL of THF was treated slowly with C12PCH2CH2PCl2 (7.32 g, 31.58 mmol, 0.45 eq) while stirring at room temperature for a period of 30 min before Et3N (35.5 g, 350.8 mmol) was added. The resulting suspension was stirred at room temperature overnight before the solution was filtered off. The resin was washed with hexane (2 X 100 mL), CH2C12 (5 X 100 mL), and hexane (5 X 100 mL).

The resulting resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): 8 148. 6 ppm. 13C NMR (75 MHz, THF-dg): for polymer-supported groups. Thereafter this will be referred to as Resin V.

A suspension of Resin V above (15.5 g, 0.67 mmol/g, 10.4 mmol) in 250 mL of THF was treated slowly with phenylmagnesium bromide (1.0 M solution in diethylether, 112 mmol). The resulting mixture was stirred at room temperature for 2 h before the solution was filtered off and the resin was washed with THF (3 X 50 mL), H20/THF (20% H20,2 X 50 mL), hexane (3 X 80 mL).

The resulting resin was dried in vacuo overnight to afford polymer-bound PhPCH2CH2PPh. 31p NMR (122 MHz, CDCl3): å 62.4 (s, br.) ppm.

Synthesis of Polymer-Bound Bisphosphinites EXAMPLE 35 A suspension of Resin V above (2.0 g, 0.99 mmol/g, 1.98 mmol) in 20 mL of THF was treated with (lS, 2S)-trans-1,2-cyclohexanediol (0.113 g, 0.973 mmol) and Et3N (1.0 g, 9.9 mmol) over a period of 5 min. The resulting mixture was stirred at room temperature for 2 days before the solution was filtered off and the resin was washed with THF (3 X 30 mL), hexane (3 X 30 mL). The resulting resin was dried in vacuo overnight to afford the polymer-bound chiral bisphosphinite. 31p NMR (122 MHz, CDC13): 8 148.2 (s, br.) ppm.

EXAMPLES 36A-36M Examples 36-A to 36-M were prepared using the procedure in Examples 34-35 with the amines, phosphines, and Grignard reagents specified in Table 4A, below. Where no Grignard reagent is specified, the procedure was discontinued at addition of the phosphine.

TABLE 4A Ex. Amine Phosphine Grignard 31PNMR 36-A (n-propyl) NH2 C12PCH2CH2PCI2 (n-butyl) MgBr 61.5 36-B (n-propyl) NH2 C12PCH2CH2PC12 (t-butyl) MgBr 3 5.3 36-C (n-propyl) NH2 C12PCH2CH2PCl BrMgCH2 (CH2) 3CH2MgBr 35.6 36-D (n-propyl) NH2 C12PCH2CH2PCI2 phenylC (CH3) 2CH2MgBr 56.2 36-E (n-propyl) NH2 Cl PCH CH2PCl 4- (t-butyl) phenylMgBr 61. 5 36-F (n-propyl) NH2 Cl PCH CH PCI 2,4,6-trimethylphenylMgBr 66.0 36-G (t-butyl) NH 2 Cl2PH2CH2PCl2 none 149.3 36-H (t-butyl) NH2 Cl PCH CH2PCl p-chlorophenylMgBr 46. 8 36-1 (t-butyl) NH2 C12PCH2CH2PCI2 phenylCH2CH2MgBr 49.2 Ex. Amine Phosphine Grignard 31PNMR 36-J (t-butyl) NH2 CI PCH CH2PCI2 i-propylMgBr 62. 4 36-K (t-butyl) NH2 C12PCH2CH2PCI2 phenoxyMgBr 137. 1 36-L (cyclohexyl) NH2 C12PCH2CH2PCt2 none. 146.0 36-M (cyclohexyl) NH2 C12PCH2CH2PCI2 BrMgCH2 (CH2) 3CH2MgBr 33.7

Cleavage of Bisphosphine Ligands from Resin EXAMPLE 37 Synthesis of cis-and trans-PhP (Cl) CH2CH2P (Cl) Ph A suspension of polymer-bound (Ph) PCH2CH2P (Ph) from Example 34 (14.6 g, 0.29 mmol/g, 4.3 mmol) and PC13 (5.0 g, 36.4 mmol) in THF (150 mL) was stirred overnight at room temperature before the resin was filtered off and washed with hexane (2 X 10 mL). Removal of solvents and excess PC13 from the filtrates by vacuum afforded 1.3 g (96% yield) of cis and trans-mixture of (Ph) P (Cl) CH2CH2P (Cl) (Ph). It was >95% pure by 1H NMR. 3 lp NMR (121 MHz, CDC13): b 93.9 (-45%), 93.3 (-55%) ppm. HRMS: Calcd for Cl4Hl4P2Cl2 (M+) : 313.9948. Found: 313.9944.

EXAMPLE 3 8 Synthesis of cis-and trans-PhP (H) CH2CH2P (H) Ph A solution of (Ph) P (Cl) CH2CH2P (Cl) (Ph) from Example 37 (cis-and trans-mixture, 1.0 g, 3.17 mmol) in 15 mL of THF was treated slowly with LiAlH4 (1.0 M in THF, 3.17 mmol) over a period of 5 min. The resulting mixture was stirred at room temperature for 2 h before 1.0 g of H20 was added to quench the reaction. After filtration, the filtrate was dried in vacuo, extracted with hexane (3 X 20 mL). Removal of solvent from extracts gave 290 mg (37%) of cis-and trans-PhP (H) CH2CH2P (H) Ph. 3 lp NMR (75 MHz, C6D6, lH-decoupled): 8 -45.4 (-40%),-45.8 (-60%) ppm. 31p NMR (75 MHz, C6D6, lH-coupled): 8-45.4 (d, Jp-H = 204.5 Hz),-45.8 (d, Jp-H = 202.9 Hz). HRMS: Calcd for C14Hl6P2 (M+) : 246.0727. Found: 246.0730.

EXAMPLE 39 Synthesis of cis-and trans- (2,4,6-Me3C6H2) P (Cl) CH2CH2P (Cl) (2,4,6-Me3C6H2) The procedure used in Example 34 was used to prepare the title compound using polymer-bound (2,4,6-Me3C6H2) PCH2CH2P (2,4,6-Me3C6H2) from Example 36-F (28.6 g, 0.286 mmol/g, 8.17 mmol) and PC13 (14.1 g, 130 mmol).

After the solvent and excess PCl3 were removed from filtrates in vacuo, 3.05 g (93% yield) of the mixture of cis-and trans-

(2,4,6-Me3H2C6) P (Cl) CH2CH2P (Cl) (2,4,6-Me3H2C6) was obtained. It was 95% pure by 1H and 31P NMR. 31P NMR (75 MHz, CDCl3): 8 92.3,91.4 ppm.

A mixture of cis-and trans- (2,4,6-Me3C6H2) P (Cl) CH2CH2P (Cl) (2,4,6-Me3C6H2) (1.0 g, 2.5 mmol) was sublimed at 170°C/10-4 torr conditions overnight. 0.25 g (25%) of trans- (2,4,6-Me3C6H2) P (Cl) CH2CH2P (Cl) (2,4,6- Me3C6H2) was obtained. It was >95% pure by 1H and 31P NMR. 31P NMR (121 MHz, CDC13): 6 92.0 ppm. iH NMR (500 MHz, CDCl3): 8 6.92 (s, 4H), 2.63 (s, 12H), 2.51 (s, 4H), 2.33 (s, 6H). 13C NMR (125 MHz, CDC13): 6 144.4, 141.6, 130. 4, 128. 6, 28. 2, 22. 4, 21. 0. HRMS : Calcd for C2oH26P2Cl2 (M+) : 398.0887. Found: 398.0875.

EXAMPLE 40 Synthesis of cis-and trans- (4-CIC6H4) P (OMe) CH2CH2P (OMe) (4-C1C6H4) A suspension of polymer-bound (4-C1C6H4) PCH2cH2P ( 4-CIC6H4) from Example 36-H (1.5 g, 0.408 mmol/g, 0.61 mmol) and MeOH (0.3 g, 9.38 mmol) in 15 mL of THF was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). After the solvent and excess MeOH were removed from filtrates by vacuum, 112 mg (49% yield) of (4-ClC6H4) P (OMe) CH2CH2P (OMe) (4-ClC6H4) was obtained. It was >95% pure by 1H NMR and GC/MS. 31P NMR (121 MHz, CDCl3): b 125.7,125.5 ppm.

1H NMR (500 MHz, CDC13): 8 7.26 (m, 8H), 3.44 (m, 6H, 2 CH3), 1.68 (m, 2H), 1.60 (m, 2H). 13C NMR (125 MHz, CDC13) : 6 141. 6, 137. 0, 132. 9, 132. 2, 132. 0, 130.9,130.3,130.1,58.3,29.1. HRMS: Calcd for Cl6Hl8P2o2Cl2 (M+) : 374.0159. Found: 374.0163.

EXAMPLE 41 Synthesis of cis-and trans- (MeCH2CH2CH2CH2) P (OMe) CH2CH2P (OMe) (CH2CH2CH2CH2Me) A suspension of polymer-bound (Cl) PCH2CH2P (Cl) (Resin V, 27.0 g, 0.48 mmol/g, 13.0 mmol) in 200 mL of THF was treated slowly with an excess of ClMg (CH2) 5MgCl (0.5 M in THF, 60 mmol) over a period of 10 min. The resulting mixture was stirred at room temperature for 2 h before the solution was filtered off. The resin was washed with THF (3 X 10 mL), H20/THF (20% H20, 2 X 10 mL), hexane (3 X 10 mL). The resulting resin was dried in vacuo overnight to afford polymer-bound Me (CH2) 4PCH2CH2P (CH2) 4Me. 31p NMR (122 MHz, CDC13): 8 6.15 (s, br.) ppm.

A mixture of polymer-bound Me (CH2) 4PCH2CH2P (CH2) 4Me (20 g, 0.476 mmol/g, 9.52 mmol) and MeOH (0.77 g, 24 mmol) in 200 mL of THF was refluxed overnight before the resin was filtered off and washed with THF (2 X

10 mL). The combined filtrates were concentrated in vacuo to afford 850 mg (30% yield) of the title compounds Me (CH2) 4P (OMe) CH2CH2P (OMe) (CH2) 4Me.

It was >95% pure by 1H NMR and GC/MS. 31P NMR (202 MHz, CDC13): 8 139.4,139.1 ppm. IH NMR (500 MHz, CDC13): 8 3.44 (d, Jp H = 10.6 Hz, 6H), 1.78-1.25 (m, 20H), 0.85 (t, J = 7.09 Hz, 6H). 13C NMR (125 MHz, CDC13): 8 56.7,33.3,32.7,26.1,23.7,22.3,13.8. HRMS: Calcd for C13H29P202 (M+-CH3) : 279.1643. Found: 279.1616.

EXAMPLE 42 Synthesis of cis-and trans- (-CH2CH2CH2CH2CH2) PH (O) CH2CH2PH (O)- A mixture of polymer-bound (-CH2CH2CH2CH2CH2) PCH2CH2P- (1.0 g, 0.327 mmol/g, 0.327 mmol, from Example 36-M) and H20 (0.5 g, 27.8 mmol) in 5 mL of THF was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The combined filtrates were concentrated in vacuo to afford 10 mg (16% yield) of the title compounds. It was >95% pure by IH NMR and GC/MS. 31P NMR (121 MHz, CDCl3, lH-decoupled): b 36.0,35.0 ppm.

31P NMR (202 MHz, CDC13, IH-coupled): 6 36.0 (d, Jp. n = 460.1 Hz), 35.0 (d, Jp-H = 457.1 Hz). 1H NMR (500 MHz, CDC13): 6 6.91 (d, Jp. n = 456.4 Hz, 1H), 6.89 (d, Jp-H = 465.4 Hz, 1H), 2.07 (m, 2H), 1.84-1.76 (m, 3H), 1.57 (m, 2H), 1.37-1.26 (m, SH), 0.84 (t, J = 7.21 Hz, 2H). 13C NMR (75 MHz, CDCl3): 6 32.7 (t, J = 7.0 Hz), 22.1,21.3,13.7. HRMS: Calcd. for C7H15P202 (M+-H): 193.0547. Found: 193.0557.

EXAMPLE 43 Synthesis of cis-and trans- (-CH2CH2CH2CH2CH2) P (OMe) CH2CH2P (OMe)- A mixture of polymer-bound (-CH2CH2CH2CH2CH2) PCH2CH2P- (0.5 g, 0.44 mmol/g, 0.22 mmol) and MeOH (0.20 g, 6.3 mmol) in 5 mL of THF was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The combined filtrates were concentrated in vacuo to afford 10 mg (21% yield) of the title compounds. 31 p NMR (121 MHz, CDC13): 8 137.6,137.4 ppm.

HRMS: Calcd. for C9H20P202 (M+): 222.0939. Found: 222.0909.

EXAMPLE 44 Synthesisof (lS, 2S)-trans-1, 2-C6HI002 P (Cl) CH2CH2P (Cl)-

A mixture of polymer-bound (1 S, 2S)-trans-1,2- OCHCH2CH2CH2CH2CHO) PCH2CH2P- from Example 35 (0.5 g, 0.48 mmol/g, 0.24 mmol) and PC13 (0.50 g, 3.64 mmol) in 5 mL of THF was stirred at room temperature overnight before the resin was filtered off and washed with THF (2 X 5 mL). The combined filtrates were concentrated in vacuo to afford 23 mg (35% yield) of the title compounds. 31p NMR (121 MHz, CDC13): 8 190.9 ppm.

EXAMPLE 45 Synthesis of (PhCH2CH2) PH (O) CH2CH2PH (O) (CH2CH2Ph) A mixture of polymer-bound (PhCH2CH2) PCH2CH2P (CH2CH2Ph) (1.5 g, 0.45 mmol/g, 0.675 mmol, from Example 36-I) and H20 (0.5 g, 27.8 mmol) in 5 mL of THF was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The combined filtrates were concentrated in vacuo to afford 65 mg (29% yield) of the title compounds. It was >95% pure by I H NMR and GC/MS. 31p NMR (202 MHz, CDCl3, lH-decoupled): 6 34.0 ppm. 31p NMR (202 MHz, CDCl3, IH-coupled) 8 34.0 (d, Jp-H = 465.4 Hz). IH NMR (500 MHz, CDC13): 8 7.2-7.1 (m, 10H), 6.87 (d, Jp. n = 465.4 Hz, 2H), 2.96-2.87 (m, 4H), 2.18-1.97 (m, 8H). 13C NMR (125 MHz, CDC13): 8 139.6,128.8, 128.1,126.8,29.6,27.7,20.8. HRMS: Calcd. for Cl8H24P2o2 (M+): 334.1252.

Found: 334.1243.

EXAMPLE 46 Synthesis of cis-and trans- (PhO) P (Ph) CH2CH2P (Ph) (PhO) A suspension of polymer-bound (Ph) PCH2CH2P (Ph) from Example 34 (2.0 g, 0.456 mmol/g, 0.913 mmol) and PhOH (0.152 g, 1.615 mmol) in 5 mL of THF was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL). The combined filtrates were concentrated in vacuo to afford 126 mg (36% yield) of the title compounds (Ph) P (OPh) CH2CH2P (OPh) (Ph). It

was >95% pure by 1H NMR and GC/MS. 31P NMR (202 MHz, CDC13): 8 121.8,121.4 ppm. 1H NMR (500 MHz, CDC13): 5 7.71-6.99 (m, 20H), 2.34-2.18 (m, 4H). 13C NMR (125 MHz, CDC13) : 6 157. 0, 140. 9, 129. 9, 129. 6, 128. 7, 122.5, 120. 2, 118. 8, 115. 7, 28. 9. HRMS : Calcd. for 430.1252. Found: 430.1282.

EXAMPLE 47 Synthesis of cis-and trans- 3, 5- (CF3) 2C6H30 P (CH2CMe2Ph) CH2CH2P [3,5- (CF3) 2C6H30 P (CH2CMe2Ph) 2 A suspension of polymer-bound (PhCMe2CH2) PCH2CH2P (CH2CMe2Ph) 2 from Example 36-D (10.0 g, 0.317 mmol/g, 3.17 mmol) and 3,5- (CF3) 2C6H30H (1.10 g, 4.78 mmol) in THF (100 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL). The filtrates were dried in vacuo to give 1.2 g (62% yield) of the title compounds. It was >95% pure by 1H NMR and GC/MS. 31P NMR (121 MHz, C6D6): 8 136.3, 135.3 ppm. 1H NMR (500 MHz, C6D6): 6 7.40-6.84 (m, 16H), 2.15 (m, 1H), 1.60 (m, 1H), 1.52 (m, 1H), 1.36-1.21 (m, 17H). 13C NMR (125 MHz, C6D6): 8 9,126.6,126.2,125.0,122.8,118.7,116.6, 115.5,51.0,37.1,31.6,29.8,29.7,28. 1. HRMS: Calcd. for C38H36P202FI2 (M+) : 814.1999. Found: 814.1954.

EXAMPLE 48 Synthesis of cis-and trans- (CH3CH2CH2S) P (Ph) CH2CH2P (Ph) (SCH2CH2CH3) A suspension of polymer-bound (Ph) PCH2CH2P (Ph) from Example 34 (20.0 g, 0.456 mmol/g, 9.13 mmol) and CH3CH2CH2SH (1.83 g, 23.6 mmol) in THF (200 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 20 mL). The filtrates were dried in vacuo to remove the solvent and excess CH3CH2CH2SH. The resulting residue was 2.69 g (78% yield) of the title compounds. It was >95% pure by IH NMR and GC/MS. 3 1 p NMR (202 MHz, C6D6): 6 29.55,29.52 ppm. IH NMR (500 MHz, C6D6): 8 7.57 (m, 4H), 7.08-7.03 (m, 6H), 2.46 (m, 4H), 2.20 (m, 4H), 1.47 (m, 4H), 0.75 (t, J = 7. 13 Hz, 6H). 13C NMR (125 MHz, C6D6): 6 138.1,130.5,127.6,126.7, 34.0,26.0 (m, Je. c = 8.75 Hz), 24.1,12.0. HRMS: Calcd. for C2oH29P2S2 (M++ H): 395.1186. Found: 395.1107.

EXAMPLE 49 Preparation of Dichloro [cis and trans-1,2-bis (l-propylthio)-(1-phenyl) phosphino] ethane] Palladium (II) A solution of (CH3CH2CH2S) P (Ph) CH2CH2P (Ph) (SCH2CH2CH3) from Example 106 (cis/trans; 50%, 0.300 g, 0.76 mmol) in 20 mL of? Cl2 was

added dropwise to a solution of PdCl2 (COD) (0.217 g, 0.76 mmol) in 25 mL of CH2Cl2 at room temperature and the solution was stirred overnight. The resulting reaction mixture was concentrated in vacuo to give solid compounds. After washed with hexane (2 X 5 mL) and dried in vacuo, 0.40 g (92% yield) of the title compounds were obtained. Recrystallization from dichloromethane/hexane (1: 1 volume ratio) gives the Dichloro trans-1,2-bis (l-propylthio)-(1-phenyl) phosphino] ethane] Palladium (II) as yellow crystals. The molecular structure of trans- (CH3CH2CH2S) P (Ph) CH2CH2P (Ph) (SCH2CH2CH3) PdCl2 has been determined by X-ray diffraction. trans-(CH3CH2CH2S) P (Ph) CH2CH2P (Ph) (SCH2CH2CH3)] PdCl2 is triclinic, P-1 (No. 2), a = 11.414 (2) A, b = 12.952 (2) A, c = 8.221 (1) A, alpha = 92.75 (1) 0, beta = 97.25 (1) 0, gamma = 98.10 (1) 0, T =-100 oc, Vol = 1190.9 A3, Z = 2, Formula weight = 571.83, Density = 1.594 g/cc, (Mo) = 13.02 cm~l. Anal. Calcd. for C2oH28P2S2PdCl2: C, 42.01; H, 4.94; Cl, 12.40. Found: C, 42.55; H, 4.57; Cl, 11.82.

Synthesis of Polymer-Bound Monophosphines EXAMPLE 50 A solution of PC13 (26 g, 189 mmol) in 400 mL of THF was treated slowly with Resin I (25 g, 1.21 mmol/g, 30.3 mmol) while stirring at room temperature for a period of 30 min. before Et3N (16 g, 157.5 mmol) was added. The resulting suspension was stirred at room temperature overnight before the solution was filtered off. The resin was washed with hexane (2 X 50 mL), CH2C12 (5 X 80 mL), and hexane (5 X 30 mL). The resulting resin was dried in vacuo overnight. 31P NMR (122 MHz, CDCl3): 6 179. 1 ppm.

A suspension of the resin above (5.0 g, 1.12 mmol/g, 5.6 mmol) in 150 mL of THF was treated slowly with phenylmagnesium bromide (2 M solution in diethylether, 64 mmol). The resulting mixture was stirred at room temperature for 30 min. before the solution was filtered off and the resin was washed with THF (3 X 50 mL), Me2CHOH/THF (20% Me2CHOH, 10 mL), hexane (3 X 30 mL).

The resulting resin was dried in vacuo overnight to afford polymer-bound PPh2.

31p NMR (122 MHz, CDCl3): 8 52.3 ppm.

EXAMPLE 51 A solution of Cl2PPh (33.8 g, 189 mmol) and Et3N (16.0 g, 157.5 mmol) in 500 mL of THF was treated slowly with Resin I (25.0 g, 1.21 mmol/g, 30.3 mmol) while stirring at room temperature for a period of 10 min. The resulting suspension was stirred at room temperature overnight before the solution was filtered off. The resin was washed with THF (50 mL), hexane (3 X 50 mL),

CH2Cl2 (4 X 50 mL), and hexane (2 X 50 mL). The resulting resin was dried in vacuo overnight. 31p NMR (122 MHz, CDCl3): 8 135.4 ppm.

A suspension of the resin (5.0 g, 1.03 mmol/g, 5.2 mmol) in 150 mL of THF was treated slowly with i-propylmagnesium chloride (0.5 M solution in diethylether, 32.0 mmol). The resulting mixture was stirred at room temperature for 2 h before the solution was filtered off and the resin was washed with THF (3 X 10 mL), Me2CHOH/THF (20% Me2CHOH, 5 mL), hexane (3 X 30 mL).

The resulting resin was dried in vacuo overnight to afford polymer-bound (i-C3H7) PPh. 31P NMR (122 MHz, CDC13): 8 55.5 ppm.

EXAMPLE 52 Example 52 was performed using the same techniques described in Examples 50 and 51. Results are shown in Table 5A below.

TABLE 5A R1 R2 31p NMR 52-A-CH2--N (n-propyl)-allyl allyl 56.9 52-B-CH2--N (n-propyl)- allyl phenyl 59.4 52-C-CH2--N (n-propyl)- chloro chloro 161. 5 52-D-CH2--N (n-propyl)-chloro phenyl 140. 3 52-E-CH2--N (n-propyl)-phenyl vinyl 60.7 52-F-CH2--N (n-propyl)- vinyl vinyl 56.1 52-G-CH2--N (phenyl)- chloro chloro 156.6 52-H-CH2--N (phenyl)- chloro ethyl 149.8 52-I-CH-N (phenyl)- cyclohexyl cyclohexyl 75.2 52-J-CH2--N (phenyl)- chloro phenyl 133.4 52-K-CH2--N (phenyl)- isopropyl isopropyl 84. 5 52-L-CH2--N (t-butyl)- allyl phenyl 44.9 52-M-CH2--N (t-butyl)- chloro chloro 179.1 52-N-CH2--N (t-butyl)- chloro phenyl 135.4 52-O-CH2--N (t-butyl)- ethyl phenyl 48.4 52-P-CH2--N (t-butyl)- isopropyl isopropyl 70.4 52-Q-CH2--N (t-butyl)- mesityl mesityl 32.9 52-R-CH2--N (t-butyl)- mesityl phenyl 42.7 L Z Rl R2 31p NMR 52-S-CH2--N (t-butyl)- phenyl vinyl 47.8 52-T-CH2--N (t-butyl)- vinyl vinyl 43. 8 52-U-CH2--N (t-butyl)- H phenyl 14.5

Cleavage of Ligands from the Polymer-Supported Monophosphines EXAMPLE 53 Synthesis of ClPPh2 A suspension of polymer-bound PPh2 from Example 50 (1.25 g, 0.98 mmol/g, 1.23 mmol) and PC13 (0.66 g, 4.8 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PC13 from the filtrates by vacuum afforded 110 mg (41% yield) of crude ClPPh2, of which the I H, 13 C and 31P NMR spectra obtained matched exactly those for authentic sample. 31p NMR (121 MHz, CDC13): õ 83. 4 ppm. IH NMR (500 MHz, CDC13): 8 7.49-7.46 (m, 4H), 7.31-7.26 (m, 6H). 13C NMR (125 MHz, CDC13): 8 138.8 (d, Jp-c = 32.6 Hz), 131.7 (d, Jp-c = 24.5 Hz), 130.4,128.6 (d, Jp-c = 6.91 Hz). HRMS: Calcd. for Cl2HloPCl (M+): 220.0209. Found: 220.0216.

EXAMPLE 54 Synthesis of ClPCy2 A suspension of polymer-bound PCy2 from Example 52 (1.0 g, 1.1 mmol/g, 1.1 mmol) and PC13 (0.66 g, 4.8 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 5 mL). Removal of solvents and excess PC13 from the filtrates by vacuum afforded 208 mg (82% yield) of crude ClPCy2, of which the I H, 13 C and 31p NMR spectra obtained matched exactly those for authentic sample. 31P NMR (121MHz, CDC13): 6 128. 8 ppm. IH NMR (500 MHz, CDCl3): 8 1.74 (m, 12H), 1.20 (m, 1OH). 13C NMR (125 MHz, CDC13): 6 38.4 (d, Jp-c = 31.4 Hz), 27.8 (d, Jp-c = 11.5 Hz), 26.9 (d, Jp-c = 9.53 Hz), 26.4.

EXAMPLE 55 Synthesis of CH3CH2CH2SPPh2 A suspension of polymer-bound PPh2 from Example 50 (1.25 g, 0.98 mmol/g, 1.23 mmol) and CH3CH2CH2SH (0.37 g, 4.8 mmol) in THF (10 mL) was refluxed overnight in a sealed reactor before the resin was filtered off and washed with THF (2 X 10 mL). After the solvent and excess CH3CH2CH2SH were removed from filtrates by vacuum, 200 mg (62% yield) of CH3CH2CH2SPPh2 was obtained. It was >95% pure by IH NMR and GC/MS.

31p NMR (202 MHz, CDC13): 6 28. 8 ppm. IH NMR (500 MHz, CDC13): 8 7.45 (m, 4H), 7.21 (m, 6H), 2.62 (m, 2H), 1.59 (m, 2H), 0.86 (t, J = 7.24 Hz, 3H). 13C NMR (125 MHz, CDC13) : 6 138. 3, 132. 4, 129. 1, 128. 3, 35. 7, 25. 0, 13. 2.

HRMS: Calcd. for CISHi7PS (M+): 260.0789. Found: 260.0793.

EXAMPLE 56 Synthesis of C1P (Ph) CH=CH2 A suspension of polymer-bound P (Ph) CH=CH2 from Example 52-E (1.0 g, 0.94 mmol/g, 0.94 mmol) and PCl3 (0.66 g, 4.8 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PC13 from the filtrates by vacuum afforded 127 mg (79% yield) of crude ClP (Ph) CH=CH2.31p NMR (121 MHz, CDC13): 8 79.9 ppm. IH NMR (500 MHz, CDC13): 8 7.59-7.35 (m, 5H), 6.58 (m, 1H), 5.91 (m, 2H). 13C NMR (125 MHz, CDC13): 6 139. 3, 138. 3, 131. 7, 130. 9, 130. 0, 128. 9. HRMS: Calcd. for C8H8PCI (M+): 170.0052. Found: 170.0041.

EXAMPLE 57 Synthesis of EtOP (CHMe2) A suspension of polymer-bound P (CHMe2) 2 from Example 51 (1.25 g, 1.06 mmol/g, 1.32 mmol, 3 lp NMR (121 MHz, CDC13): 8 70.4 ppm) and EtOH (0.22 g, 4.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL). After the solvents were removed from filtrates by vacuum, 55 mg (26% yield) of EtOP (CHMe2) was obtained. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDC13): 8 151.4 ppm. IH NMR (500 MHz, CDC13): 8 3.71 (m, 2H), 1.15 (m, 3H), 1.00 (m, 12H).

13C NMR (125 MHz, CDC13): HRMS: Calcd. for C8HI9PO (M+): 162.1174. Found: 162.1175.

EXAMPLE 58 Synthesis of CH3CH2CH2SP (CHMe2) 2 An analogous procedure to that for EtOP (CHMe2) was used for the synthesis of title compound using polymer-bound P (CHMe2) 2 from Example 51 (1.25 g, 1.06 mmol/g, 1.32 mmol) and CH3CH2CH2SH (0.37 g, 4.8 mmol). After the solvents were removed from filtrates by vacuum, 250 mg (98% yield) of CH3CH2CH2SP (CHMe2) was obtained. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDCl3): 6 65. 7 ppm. tH NMR (500 MHz, CDC13): b 2.48 (m, 2H), 1.81 (m, 2H), 1.59 (m, 2H), 1.07 (m, 12H), 0.90 (t, J = 7.33 Hz, 3H). 13C NMR (125 MHz, CDC13) : 6 36. 3, 25. 1, 19. 2, 18. 2, 12. 9.

EXAMPLE 59 Synthesis of (Me2CH) PH (O) (CHMe2) A suspension of polymer-bound P (CHMe2) 2 from Example 51 (1.25 g, 1.06 mmol/g, 1.32 mmol) and H20 (0. 1 g, 4.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess H20.

The resulting residue was 50 mg (28% yield) of (Me2CH) PH (O) (CHMe2). It was >95% pure by IH NMR and GC/MS. 31P NMR (121 MHz, CDC13, IH-decoupled): 6 56. 9 ppm. 31p NMR (121 MHz, CDC13, IH-coupled): 8 24.1 (d, Jp-H = 429.7 Hz). IH NMR (500 MHz, CDC13): 8 6.30 (d, Jp-H = 434.1 Hz, 1H), 1.92 (m, 2H), 1.15 (m, 12H). 13C NMR (125 MHz, CDC13): 8 25.0 (d, Jp-C = 63.9 Hz), 16.0,14.8. HRMS: Calcd. for C6HlsPO (M+): 134.0861. Found: 134.0856.

EXAMPLE 60 Synthesis of CH3CH2CH2SP (Ph) (2,4,6-Me3H2C6) A suspension of polymer-bound PPh (2,4,6-Me3H2C6) from Example 52-R (1.25 g, 0.95 mmol/g, 1.18 mmol, 31P NMR (121 MHz, CDC13): 5 42.7 ppm) and CH3CH2CH2SH (0.37 g, 4.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess CH3CH2CH2SH. The resulting residue was 350 mg (98 % yield) of CH3CH2CH2SP (Ph) (2,4,6- Me3H2C6). It was >95% pure by 1H NMR and GC/MS. 31P NMR (121 MHz, CDC13): 8 20.6 ppm. 1H NMR (500 MHz, CDC13): 8 7.31 (m, 2H), 7.13 (m, 3H), 6.79 (s, 2H), 2.72 (m, 2H), 2.26 (s, 6H), 2.17 (s, 3H), 1.67 (m, 2H), 0.92 (t, J = 7. 31Hz, 3H). 13C NMR (125 MHz, CDC13): 6 144.0,140.9,140.2,132.0,129.7,129.4,128.2,127.1,38.0,25.5,23 .3,21.2,13.

4. Calcd for C1gH23Ps (M+): 302.1258. Found: 302.1266.

EXAMPLE 61 Synthesis of (2,4,6-Me3H2C6) PH (O) (Ph) Scale-up preparation was carried out using the following procedure. A suspension of polymer-bound P (Ph) Cl from Example 52 (15.0 g, 1.03 mmol/g, 15.4 mmol) in 200 mL of THF was treated with Me3C6H2MgCl (98 mmol, 2M solution in THF) over a period of 10 min. The resulting mixture was stirred for an additional 2 h at ambient temperature before the solution was filtered off and the resin was washed with THF (3 X 20 mL), Hexane (3 X 20 mL), Me2CHOH (2 X 15 mL), Hexane (2 x 20 mL). A suspension of the resin above (ca. 15 g) and H20 (3.6 g, 200 mmol) in 200 of THF was refluxed overnight. The mixture was cooled

to room temperature, and the resulting resin was filtered off and washed with Hexane (2 X 20 mL). The filtrates were evaporated to dryness and the residue was sublimed at 150 °C/10-4 torr conditions to afford 2.0 g (53% yield) of the title compound. 31P NMR (121 MHz, CDCl3, IH-decoupled): õ 18.0.31P NMR (121 MHz, CDC13, IH-coupled): 8 18.0 (d, Jp-H = 512.1 Hz). IH NMR (500 MHz, CDC13): 8 8.55 (d, Jp-H = 512.1 Hz, 1H), 7.57 (m, 2H), 7.48 (m, 1H), 7.35 (m, 2H), 6.80 (d, Jp-C = 4.0 Hz, 2H), 2.29 (s, 6H), 2.23 (s, 3H). 13C NMR (125 MHz, CDC13): 8 144.8,143.3,133.5,131.5,131.0,129.5,128.0,120.7,22.1,21.9.

HRMS: Calcd. for Cl5Hl7PO (M+): 244.1017. Found: 244.1015. Anal. Calcd. for CgHz3PO: C, 73.76; H, 7.01 ; P, 12.68. Found: C, 73.66; H, 6.92; P, 12.70.

EXAMPLE 62 Synthesis of CH3CH2CH2SP (Ph) (CHMe2) A suspension of polymer-bound PPh (CHMe2) from Example 51 (1.25 g, 1.02 mmol/g, 1.28 mmol, 31p NMR (121 MHz, CDC13): 5 55.5 ppm) and CH3CH2CH2SH (0.37 g, 4.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess CH3CH2CH2SH. The resulting residue was 280 mg (97 % yield) of CH3CH2CH2SP (Ph) (CHMe2). It was >95% pure by IH NMR and GC/MS. 31P NMR (121 MHz, CDC13): 8 45.2 ppm. 1H NMR (500 MHz, CDC13): 8 7.55 (m, 2H), 7.28 (m, 3H), 2.58 (m, 2H), 1.99 (m, 1H), 1.58 (m, 2H), 1.04 (m, 2H), 0.97-0.81 (m, 9H). 13C NMR (125 MHz, CDC13): 8 138.1,132.0,131.1,128.2,35.6,34.5,29.6,19.0,13.0. Calcd. for C12H19PSO (MO+): 242.0894. Found: 242.0883.

EXAMPLE 63 Synthesis of (Me2CH) PH (O) (Ph) A suspension of polymer-bound PPh (CHMe2) from Example 51 (1.25 g, 1.02 mmol/g, 1.28 mmol, 31P NMR (121 MHz, CDC13): 8 55.5 ppm) and H20 (0.1 g, 4.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess H20. The resulting residue was 80 mg (37 % yield) of (Me2CH) PH (O) (Ph). It was >95% pure by IH NMR and GC/MS. 3 lp NMR (121 MHz, CDCl3, lH-decoupled): 8 47.8.3 1 P NMR (121 MHz, CDCl3, 1H-coupled): 8 47.8 (d, Jp-H = 487.7 Hz). IH NMR (500 MHz, CDCl3): 8 7.44-7.53 (m, 5H), 7.25 (d, Jp-H = 487.5 Hz, 1H), 2.33 (m, 1H), 1.12 (m, 6H).

13C NMR (125 MHz, CDC13): HRMS: Calcd for CgHI3PO (M+): 168.0704. Found: 168.0704.

Synthesis of Polymer-Bound Bidentate Ligands EXAMPLE 64 Polymer-Bound P (Ph) CH2CH2P (Ph) 2 A suspension of polymer-bound P (Ph) CH=CH2 from Example 52-E (1.0 g, 0.94 mmol), Ph2PH (2.1 g, 11.3 mmol) and NaO-tBu (0.1 g, 1.0 mmol) in 10 mL of THF was refluxed overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 50 mL), CH2C12 (5 X 80 mL), Me2CHOH (2 X 5 mL) and hexane (5 X 30 mL). The resin was dried in vacuo overnight. 31p NMR (122 MHz, CDC13): 8 62.7,-11.3 ppm.

EXAMPLE 65 Polymer-Bound P (Ph) CH2CH2P (Ph) Me A suspension of polymer-bound P (Ph) CH=CH2 from Example 52-S (1.7 g, 1.76 mmol, 1.04 mm/g), Ph (Me) PH (2.0 g, 14.5 mmol) and NaO-tBu (0.1 g, 1.0 mmol) in 10 mL of THF was refluxed overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 50 mL), CH2C12 (5 X 80 mL), Me2CHOH (2 X 5 mL) and hexane (5 X 30 mL). The resin was dried in vacuo overnight. 31p NMR (122 MHz, CDC13): 8 45.8,-31.7 ppm.

EXAMPLE 66 Polymer-Bound l-P (Ph)-2-C6H4OMe A suspension of polymer-bound P (Ph) Cl from Example 52-D (2.0 g, 1.86 mmol, 0.93 mm/g), and 1, 2-MeOC6H4MgBr (15.0 mmol, 0.5 M in THF solution) in 10 mL of THF was refluxed over 2 h before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2C12 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDCl3): 6 57. 3 ppm.

EXAMPLE 67 Polymer-Bound 1-P (Ph)-2,4-C6H3 (OMe) 2 A suspension of polymer-bound P (Ph) Cl Example 52-D (2.0 g, 1.86 mmol, 0.93 mm/g), and 1,2,4- (MeO) 2C6H3MgBr (15.0 mmol, 0.5 M in THF solution) in 10 mL of THF was refluxed over 2 h before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31p NMR (122 MHz, CDC13): 8 56.1 ppm.

EXAMPLE 68 Polymer-Bound l-P (Ph)-3-C6H4OMe A suspension of polymer-bound P (Ph) Cl Example 52-N (0.8 g, 0.88 mmol, 0.95 mm/g), and 1, 3-MeOC6H4MgBr (4.0 mmol, 0.5 M in THF

solution) in 10 mL of THF was stirred at room temperature over 2 h before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2C12 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDCl3): 8 52. 8 ppm EXAMPLE 69 Polymer-Bound l-P (Ph)-2-C6H4SMe A suspension of polymer-bound P (Ph) Cl Example 52-D (2.0 g, 1.86 mmol, 0.93 mm/g), and 1, 2-MeSC6H4ZnI (15.0 mmol, 0.5 M in THF solution) in 10 mL of THF was refluxed overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): 8 56. 9 ppm.

EXAMPLE 70 Polymer-Bound 1-P (Ph)-8-N, N-Dimethylnaphthylamine A solution of N, N, N', N'-tetramethylethylenediamine (2.04 g, 17.6 mmol) in 15 mL of hexane was treated with n-butyllithium (9.28 mmol, 1.6 M solution in Hexane) dropwise over a period of 5 min, the solution was stirred an additional 15 min before N, N-dimethyl-l-naphthylamine (4.0 g, 23.4 mmol) was added. The resulting mixture was stirred at room temperature overnight before a polymer- bound P (Ph) Cl Example 52-D (1.0 g, 0.93 mmol, 0.93 mm/g) was added to the reaction mixture. The resulting suspension was stirred overnight before solution was filtered off and resin was washed with hexane (2 X 10 mL), CH2C12 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDCl3): 6 65. 0 ppm.

EXAMPLE 71 Polymer-Bound P (Ph)-2- (R)-N, N-Dimethyl-l'-Ferrocenylethyl amine A solution of N, N, N', N'-tetramethylethylenediamine (0.22 g, 1.89 mmol) in 5 mL of hexane was treated with n-butyllithium (1.28 mmol, 1.6 M solution in Hexane) dropwise over a period of 5 min, the solution was stirred an additional 15 min before (R)- (+)-N, N-dimethyl-l-ferrocenylethylamine (0.5 g, 1.89 mmol) was added. The resulting mixture was stirred at room temperature overnight before a polymer-bound P (Ph) Cl (0.5 g, 0.466 mmol, 0.93 mm/g, Example 52-D) was added to the reaction mixture. The resulting suspension was stirred overnight before solution was filtered off and resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): b 52.5 ppm.

EXAMPLE 72 Polymer-Bound P (Et)-2- (R)-NN-Dimethyl-l'-Ferrocenylethyl amine A similar procedure to those described above was used to synthesize the title compound using N, N, N', N'-tetramethylethylenediamine (0.80 g, 6.88 mmol), n-butyllithium (4.8 mmol, 1.6 M solution in Hexane), (R)- (+)-N, N-dimethyl-l- ferrocenylethylamine (1.5 g, 5.66 mmol) and a polymer-bound P (Et) Cl from Example 52-H (2.3 g, 2.16 mmol, 0.94 mm/g). 31P NMR (122 MHz, CDCl3): 8 35.4 ppm.

EXAMPLE 73 Polymer-Bound P (Ph)-2-C4H3S A suspension of polymer-bound P (Ph) Cl from Example 52-N (0.8 g, 0.82 mmol, 1.03 mm/g), and 2-thienyllithium (5.0 mmol, 2 M in THF solution) in 10 mL of THF was stirred at room temperature over 2 h before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDCl3): 5 37. 0 ppm.

EXAMPLE 74 Polymer-Bound P (Ph)-2-C3H2SN A suspension of polymer-bound P (Ph) Cl from Example 52-D (2.0 g, 1.86 mmol, 0.93 mm/g), and 2-thiazolezinc bromide (15.0 mmol, 0.5 M in THF solution) in 10 mL of THF was refluxed overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2C12 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDCl3): 8 56. 2 ppm.

EXAMPLE 75 Polymer-Bound P (Ph)-2-C5H4N A suspension of polymer-bound P (Ph) Cl from Example 52-D (3.0 g, 2.79 mmol, 0.93 mm/g), and 2-pyridylmagnesium bromide (15 mmol, 0.5 M in THF solution) in 20 mL of THF was stirred at room temperature overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): b 63.4 ppm.

EXAMPLE 76 Polymer-Bound P (Ph) CH2CH2PPh2 by Hydrophosphinations A suspension of polymer-bound N (CH2CH2Me) P (Ph) H from Example 52-U (0.8 g, 0.80 mmol, 1.0 mm/g) and diphenylvinylphosphine (1.5 g, 7.06 mmol) in 20 mL of toluene was refluxed overnight before the solution was

filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31p NMR (122 MHz, CDC13): 8 62.7,-11.4 ppm.

EXAMPLE 77 Polymer-Bound P (Ph) CH2CH2SPh A suspension of polymer-bound N (Ph) P (Ph) CH=CH2 from Example 52-J (2.0 g, 2.0 mmol, 1.0 mm/g) and EtS-SEt (1.0 g, 8.18 mmol) in 20 mL of THF was refluxed for 2 days before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): 8 70.9 ppm.

Cleavage of Bidentate Ligands from Resin EXAMPLE 78 Synthesis of PhP (Cl) CH2CH2PPh2 A suspension of polymer-bound PhPCH2CH2PPh2 (1.0 g, 0.80 mmol, prepared as in Example 5 using n-propylamine and phenylMgBr, 31 P NMR 62.7, -11.3 ppm) and PC13 (0.75 g, 5.46 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PC13 from the filtrates by vacuum afforded 160 mg (56% yield) of crude PhP (Cl) CH2CH2PPh2. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDCl3): 6 93.9 (d, J = 30. 2 Hz),-11.8 (d, J = 30. 4 Hz) ppm. 1H NMR (S00 MHz, CDC13): 8 7.53-7.16 (m, 15H), 2.05 (m, 4H). 13CNMR (125 MHz, 129.1, 128. 9, 128. 7, 32. 8, 22. 5. HRMS : Calcd. for C20Hs9P2Cl (M+): 356.0651.

Found: 356.0650.

EXAMPLE 79 Synthesis of PhPH (O) CH2CH2PMe (Ph) A suspension of polymer-bound PhPCH2CH2PMe (Ph) (1.0 g, 0.92 mmol, prepared as in Example 65,31p NMR 47.9,-31.2 ppm) and H20 (0.75 g, 41.7 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess H20 from the filtrates by vacuum afforded 100 mg (39% yield) of crude PhPH (O) CH2CH2PMe (Ph). It was >95% pure by IH NMR and GC/MS. 31p NMR (202 MHz, CDC13): 8 29.2 (d, J = 38.1 Hz),-30.0 (d, J = 38.1 Hz); 29.0 (d, J = 38. 6 Hz),-30.3 (d, J = 38. 7 Hz) ppm. 31P NMR (202 MHz, CDCl3, IH-coupled): 8 29.1 (d, Jp-H = 440.4 Hz),-30.0; 29.1 (d, Jp-H = 440.4 Hz), -30.3 ppm.

EXAMPLE 80 Synthesis of!-PhP (Cl)-2-MeOC6H4 A suspension of polymer-bound 1-PPh-2-MeOC6H4 (2.0 g, 0.873 mmol/g, 1.746 mmol, prepared as in Example 66,31p NMR 57.3) and PCl3 (1.3 g, 9.49 mmol) in 15 mL of THF was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PCl3 from the filtrates by vacuum afforded 325 mg (74% yield) of crude!-PhP (Cl)-2-MeOC6H4. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDC13): 6 78. 3 ppm. IH NMR (500 MHz, CDC13): b 7.45 (m, 3H), 7.22 (m, 4H), 6.91 (m, 1H), 6.68 (m, 1H), 3.54 (s, 3H).

13C NMR (125 MHz, CDCl3): # 160.5, 139.0, 132.2, 131.7, 131.6, 130.4, 128.5, 126.3,121.5,110.8,55.9. HRMS: Calcd. forCI3Hl2PClo (M+): 250.0314.

Found: 250.0311.

EXAMPLE 81 Synthesis of!-PhP (Cl)-2,4- (MeO) 2C6H3 A suspension of polymer-bound l-PPh-2, 4- (MeO) 2C6H3 (2.0 g, 0.85 mmol/g, 1.70 mmol, prepared as in Example 57,31p NMR 56.1) and PC13 (1.3 g, 9.49 mmol) in 15 mL of THF was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PC13 from the filtrates by vacuum afforded 450 mg (94% yield) of crude 1-PhP (Cl)-2,4- (MeO) 2C6H3. It was >95% pure by IH NMR and GC/MS. 31PNMR (202 MHz, CDC13): 6 78. 8 ppm. IH NMR (500 MHz, CDC13): b 7.43 (m, 2H), 7.22 (m, 4H), 6.38 (m, IH), 6.27 (m, 1H), 3.62 (s, 3H), 3.55 (s, 3H). 13CNMR (125 MHz, 129. 9, 128. 2, 117. 4, 105. 7, 98. 3, 55. 7, 55. 3. HRMS : Calcd. for C14H14pC102 (M+): 280.0420. Found: 280.0421.

EXAMPLE 82 Synthesis of!-PhP (Cl)-3-MeOC6H4 A suspension of polymer-bound 1-PPh-3-MeOC6H4 (0.8 g, 0.95 mmol/g, 0.76 mmol, prepared as in Example 58,31P NMR 52.8) and PC13 (0.56 g, 4.1 mmol) in 15 mL of THF was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PC13 from the filtrates by vacuum afforded 80 mg (42% yield) of crude l-PPh (Cl)-3-MeOC6H4. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDC13): 8 83. 3 ppm. IH NMR (500 MHz, CDC13): 57.05 (m, 2H), 7.30 (m, 3H), 7.21 (m, 1H), 7.06 (m, 2H), 6.83 (m, 1H), 3.68 (s, 3H). 13C NMR (125 MHz, CDC13): 6159. 8, 140. 4, 139. 0, 132. 0, 130. 6, 129. 9, 128. 8, 124. 1,

117.1,116.4,55.5. HRMS: CalcdforCI3Hl2PClO (M+): 250.0314. Found: 250.0322.

EXAMPLE 83 Synthesis of 2-PhP (Cl) C4H3S A suspension of polymer-bound 2-PhPC4H3S (0.8 g, 0.98 mmol/g, 0.78 mmol, from Example 73,31P NMR 37.0) and PCl3 (0.56 g, 4.1 mmol) in 10 mL of THF was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PC13 from the filtrates by vacuum afforded 80 mg (45% yield) of crude 2-PhP (Cl) C4H3S. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDC13): 8 66.8 ppm. IH NMR (500 MHz, CDC13): 8 7.67-7.61 (m, 3H), 7.43 (m, 1H), 7.36 (m, 3H), 7.03 (m, 1H). 13C NMR (125 MHz, CDC13): 8 140.9,138.4,136.6,134.2,130.8,130.3,128.4,127.7. HRMS: Calcd. for CioHgPCISO (MO+): 241.9722. Found: 241.9739.

Synthesis of Polymer-Bound Tridentate Ligands EXAMPLE 84 Polymer-Bound P (CH2CH2PPh2) 2 A suspension of polymer-bound P (CH=CH2) 2 (2.0 g, 0.985 mm/g, 1.97 mmol, from Example 52-F), Ph2PH (5.5 g, 29.6 mmol) and NaO-tBu (0.1 g, 1.0 mmol) in 15 mL of THF was refluxed overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (2 X 5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDCl3): 6 65.6,-12.0 ppm.

EXAMPLE 85 Polymer-Bound P CH2CH2P (Ph) Me] 2 A suspension of polymer-bound P (CH=CH2) 2 (1. 0 g, 0.985 mmol, from Example 52-F), Ph (Me) PH (1.5 g, 10.9 mmol) and NaO-tBu (0.05 g, 0.5 mmol) in 10 mL of THF was refluxed overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (2 X 5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): 864.8,-31.5 ppm.

EXAMPLE 86 Polymer-Bound P (C4H30) (Br) A solution of furan (7.0 g, 102.8 mmol) and PBr3 (25.0 g, 92.4 mmol) in 30 ml of pyridine was refluxed over 5 h before the resulting mixture was cooled to room temperature and 100 mL of hexane was added. This crude products exhibit a single 31 P NMR peak at 103.5 ppm. After filtered off the solids, the hexane was

removed from the filtrate by vacuum, a polymer-bound NH (CH2CH2Me) prepared as in Example 1 (10 g, 11.0 mmol, 1.1 mm/g) was added to the solution above. The resulting suspension was stirred overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 30 mL), CH2Cl2 (5 X 30 mL), THF (2 X 30 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31p NMR (122 MHz, CDC13): 6 113.1 ppm.

EXAMPLE 87 Polymer-Bound P (C4H30) (C4H3S) A suspension of polymer-bound P (C4H30) (Br) from Example 86 (1.0 g, -1.0 mmol) in 15 mL of THF was treated slowly with 2-thienyllithium (10.0 mmol, 1.0 M solution in THF) over a period of 5 min. The resulting mixture was stirred for 2 h at room temperature before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2C12 (5 X 10 mL), Me2CHOH (2 X 5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): 6 28. 4 ppm.

EXAMPLE 88 Polymer-Bound P (C5H4N) 2 A suspension of polymer-bound PC12 (2.0 g, 0.968 mm/g, 1.94 mmol, from Example 52-C) in 15 mL of THF was treated slowly with 2-pyridylzinc bromide (15 mmol, 0.5 M solution in THF) over a period of 5 min. The resulting mixture was refluxed overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (2 X 5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31p NMR (122 MHz, CDCl3): 8 59.0 ppm.

EXAMPLE 89 Polymer-Bound P (2-C6H4SMe) 2 A suspension of polymer-bound PCl2 (2.0 g, 0.968 mm/g, 1.94 mmol, from Example 52-C) in 15 mL of THF was treated slowly with 2- (thiomethyl)- phenylzinc iodide (15 mmol, 0.5 M solution in THF) over a period of 5 min. The resulting mixture was refluxed overnight before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (2 X 5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDCl3): 8 49. 6 ppm.

EXAMPLE 90 Polymer-Bound P (2-C6H4OMe) 2 A suspension of polymer-bound PCl2 (2.0 g, 0.968 mm/g, 1.94 mmol, from Example 52-C) in 15 mL of THF was treated slowly with 2-methoxy-

phenylmagnesium bromide (15 mmol, 0.5 M solution in THF) over a period of 5 min. The resulting mixture was refluxed for 3 h before the solution was filtered off. The resulting resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (2 X 5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): 6 48. 5 ppm.

EXAMPLE 91 Polymer-Bound P (8-C l oH6NMe2) 2 A solution of N, N, N', N'-tetramethylethylenediamine (2.1 g, 18.1 mmol) in 15 mL of hexane was treated with n-butyllithium (12.8 mmol, 1.6 M solution in Hexane) dropwise over a period of 5 min, the solution was stirred an additional 15 min before N, N-dimethyl-l-naphthylamine (5.0 g, 29.2 mmol) was added to the reaction solution. The resulting mixture was stirred at room temperature overnight before a polymer-bound PCl2 (1.0 g, 0.97 mmol, from Example 52-C) was added to the reaction mixture. The resulting suspension was stirred overnight before solution was filtered off and resin was washed with hexane (2 X 10 mL), CH2Cl2 (5 X 10 mL), Me2CHOH (5 mL) and hexane (5 X 10 mL). The resin was dried in vacuo overnight. 31P NMR (122 MHz, CDC13): 6 70. 0 ppm.

Cleavage of Tridentate Ligands from Resin EXAMPLE 92 Synthesis of Ph2PCH2CH2PH (O) CH2CH2PPh2 A suspension of polymer-bound P (CH2CH2PPh2) 2 (1.0 g, 0.72 mmol, from Example 84) and H20 (0.5 g, 27.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL).

Removal of solvents and excess H20 from the filtrates by vacuum afforded 127 mg (37% yield) of crude Ph2PCH2CH2PH (O) CH2CH2PPh2. It was >95% pure by IH NMR and GC/MS. 3 lp NMR (202 MHz, CDCl3): 6 36.4 (dd, J = 43.5 Hz),-11.7 (d, J = 43.5 Hz) ppm. 31P NMR (202 MHz, CDC13, IH-coupled): 6 36.2 (d, Jp-H = 455.3 Hz),-11.7 ppm. IH NMR (500 MHz, CDCl3): 8 7.68-7.19 (m, 20H), 6.81 (d, Jp-H = 452.6 Hz, 1H), 2.50-1.73 (m, 8H). 13C NMR (125 MHz, CDCl3): 6 136.9,132.7,131.5,128.8,24.3,19.5.

EXAMPLE 93 Synthesis of PhP (Me) CH2CH2PH (O) CH2CH2P (Me) Ph A suspension of polymer-bound P [CH2CH2P (Me) Ph] 2 (1. 0 g, 0.79 mmol, from Example 85) and H20 (0.4 g, 22.2 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL).

Removal of solvents and excess H20 from the filtrates by vacuum afforded 200 mg (72% yield) of crude PhP (Me) CH2CH2PH (O) CH2CH2P (Me) Ph. It was >95%

pure by IH NMR and GC/MS. 3 lp NMR (202 MHz, CDCl3): 6 37.2 (t, J = 36.1 Hz),-30.2 (dd, 3J = 36.3 Hz, 6J = 4.7 Hz, 6J = 4.4 Hz),-30.5 (dd, 3J = 36.3 Hz, 6J = 3.2 Hz, 6J = 3.6 Hz) ppm. 31P NMR (202 MHz, CDC13, IH-coupled): 8 37.2 (d, Jp-H = 454.7 Hz),-30.2 (d, J = 36.5 Hz),-30.5 (d, J = 37.1 Hz) ppm. IH NMR (500 MHz, CDC13): 8 7.39-7.17 (m, 10H), 6.72 (d, Jp-H = 453.8 Hz, 1H), 1.79-1.65 (m, 8H), 1.26 (s, 6H). 13C NMR (125 MHz, CDCl3): 8 137.9,131.4, 128.9, 128. 3, 23. 9, 21. 6, 10. 8. HRMS : Calcd. for Cl8H25P3o3 (Mo2+) : 382.1017. Found: 382.0954.

EXAMPLE 94 Synthesis of C4H30-PH (O)-C4H3S A suspension of polymer-bound P (C4H30) (C4H3S) (0.6 g, 0.54 mmol, 0.899 mm/g, from Example 87) and H20 (0.5 g, 27.7 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess H20 from the filtrates by vacuum afforded 16 mg (15% yield) of crude C4H30-PH (O)-C4H3S. It was >95% pure by IHNMRandGC/MS. 31PNMR (122 MHz, CDC13): 8-6.66 ppm. 31P NMR (122 MHz, IH-coupled, CDCl3): 8-6.66 (d, Jp-H = 515.5 Hz) ppm.

EXAMPLE 95 Synthesis of 2-MeSC6H4P (Cl)-2-MeSC6H4 A suspension of polymer-bound PIC6H4 (SMe) 212 (1.0 g, 0.83 mmol) and PCl3 (0.75 g, 5.47 mmol, from Example 89) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PCl3 from the filtrates by vacuum afforded 205 mg (79% yield) of crude 2-MeSC6H4P (Cl)-2-MeSC6H4. It was >95% pure by 1H NMR and GC/MS. 3 IP NMR (202 MHz, CDC13): 8 57.3 ppm.

IH NMR (500 MHz, CDC13): 8 7.40 (m, 2H), 7.32 (m, 4H), 7.20 (m, 2H), 2.34 (s, 6H). 13C NMR (125 MHz, CDC13): 8 141.7,140.5,132.6,131.1,130.0, 127.5,19.0. HRMS: Calcd. for C14Hl4PClS2 (M+): 311.9963. Found: 311.9970.

EXAMPLE 96 Synthesis of 2-MeOC6H4P (Cl)-2-MeOC6H4 A suspension of polymer-bound P C6H4 (OMe) 2 2 (2.0 g, 1.65 mmol, 0.83 mm/g, from Example 90) and PC13 (1.3 g, 7.30 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess PCl3 from the filtrates by vacuum afforded 400 mg (86% yield) of crude 2-MeOC6H4P (Cl)-2-MeOC6H4. It was >95% pure by IH NMR and GC/MS. zip NMR (202 MHz, CDC13): 8

70.8 ppm. IH NMR (500 MHz, CDC13): b 7.30 (m, 4H), 6.90 (m, 2H), 6.80 (m, 2H), 3.73 (s, 6H). 13CNMR (125 MHz, 121.5,110.9,56.2. HRMS: Calcd. for C14H14PClO2(M+) : 280.0420. Found: 280.0429.

EXAMPLE 97 Synthesis of 8-Me2NCI0H6PH (O)-8-Me2NCl0H6 A suspension of polymer-bound P 8-Me2NCgH6) 2 (1. 0 g, 0.77 mmol, from Example 91) and H20 (0.5 g, 27.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL).

Removal of solvents and excess H20 from the filtrates by vacuum afforded 115 mg (3 8% yield) of crude 8-Me2NCz0H6PH (o)-8-Me2NcloH6. 3 lp NMR (202 MHz, CDC13): 6 15.7 ppm. 31p NMR (202 MHz, CDC13, IH-coupled): 8 15.7 (d, Jp-H = 605.8 Hz) ppm.

Cleavage of Diphosphine Ligands from Resin EXAMPLE 98 Synthesis of 1- (diethylphosphino)-2 (ethoxylethylphosphinite) ethane A suspension of polymer-bound (Et) PCH2CH2P (Et) 2 (1.0 g,-0.899 mmol/g,-0.90 mmol, prepared as in Example 5) and EtOH (0.41 g, 9.1 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL). Removal of solvents and excess EtOH from the filtrates by vacuum afforded 162 mg (81% yield) of (EtO) (Et) PCH2CH2P (Et) 2. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, C6D6): 5 135.8 (d, J = 20. 5 Hz),-18.2 (d, J = 20. 2 Hz). IH NMR (500 MHz, C6D6): 6 3.76 (m, 2H), 1.81 (m, 2H), 1.66 (m, 4H), 1.48 (m, 2H), 1.36 (m, 4H), 1.22-1.07 (m, 12H). ¹³C NMR (125 MHz, C6D6) : 8 67. 2, 30. 2, 27. 1, 21. 8, 20. 5, 18. 8, 1 l. l, 9. 5. HRMS : Calcd. for C8H19P2O (M+-Et) : 193.0911. Found: 193.0922.

EXAMPLE 99 Synthesis of 1- (diisobutylphosphino)-2- (ethoxylisobutylphosphinite) ethane A similar procedure to that described above in Example 98 was used to prepare the title compound using polymer-bound (Me2CHCH2) PCH2CH2P (CH2CHMe) 2 (1.17 g,-0.82 mmol/g,-0.96 mmol, prepared as in Example 5) and EtOH (0.27 g, 6.0 mmol). After the solvents were removed from filtrates by vacuum, 70 mg (24% yield) of (EtO) (Me2CHCH2) PCH2CH2P (CH2CHMe) 2 was obtained. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDCl3): 6 132.5 (d, J = 20.4 Hz), -33.5 (d, J = 20.4 Hz). IH NMR (500 MHz, CDCl3): 6 3.66 (m, 2H), 1.79 (m, 1H), 1.63 (m, 4H), 1.43 (m, 2H), 1.26-1.13 (m, 8H), 1.03-0.92 (m, 19H). 13C

(125 MHz, CDCl3): 8 65.6,43.4,38.6,29.1,26.3,25.2,24.6,24.3,23.8,22.1, 17.2. MS (rel. abundance): M+-Et (6), M+-EtO (10), 221.1 (100). HRMS: Calcd. for C14H3lP20 (M+-Et): 277.1850. Found: 277.1846.

EXAMPLE 100 Synthesis of 1- (diphenylphosphino)-2- (ethoxylphenylphosphinite) ethane A suspension of polymer-bound (Ph) PCH2CH2P (Ph) 2 (13.6 g, -0.74 mmol/g,-10.1 mmol, prepared as in Example 5) and EtOH (5 g, 109 mmol) in THF (200 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 10 mL). The filtrate was dried in vacuo to remove the solvent and excess EtOH, the residue was extracted with 3 x 20 mL of hexane.

The combined hexane extracts were dried under reduced pressure to give 2.17 g (59 % yield) of (Ph) (EtO) PCH2CH2P (Ph) 2. It was >95% pure by IH NMR and GC/MS. 31P NMR (122 MHz, C6D6): 6 120. 4,-11.6 ppm. IH NMR (500 MHz, C6D6): 8 7.59-7.13 (m, 15H), 3.69 (m, 2H), 2.3-2.0 (m, 2H), 1. 1 (t, J = 7.0 Hz).

13C NMR (125 MHz, C6D6): 6 145.4,141.5,131.8,131.5,131.0,130.9,130.7, 130.5, 67. 9, 34. 1, 24. 3, 19. 5 HRMS : Calcd. forC22H24P20 : 366.1302. Found: 366.1306.

EXAMPLE 101 Synthesis of 1- di (4-fluorophenyl) phosphino-2- ethoxyl (4-fluoro phenyl) phosphinite) ethane An analogous procedure to that for (Et) (EtO) PCH2CH2P (Et) 2 was used for the synthesis of title compound using polymer-bound (4-FC6H5) PCH2CH2P (4- FC6H5) 2 (1.28 g,-0.75 mmol/g,-0.96 mmol, prepared as in Example 5) and EtOH (0.27 g, 6.0 mmol). After the solvents were removed from filtrates by vacuum, 110 mg (27% yield) of (EtO) (4-FC6H5) PCH2CH2P (4-FC6H5) 2 was obtained. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDC13): 8 119.2 (d, J = 28.5 Hz),-14.0 (d, J = 28.5 Hz). 19F (377 MHz CDC13): 6 112.0,112.6. IH NMR (500 MHz, CDC13) : 6 7.36 (m, 2H), 7.19 (m, 4H), 7.00 (m, 2H), 6.92 (m, 4H), 3.66 (m, 2H), 1.90 (m, 2H), 1.70 (m, 1H), 1.58 (m, 1H), 1.14 (t, J = 6.99 Hz, 3H). 13C (125 MHz, CDCl3): 6 164.6,164.3,162.6,162.2, 134.3,133.5,131.3,115.9,65.7,30.9,21.6,17.1. HRMS: Calcd. for C22H2iP20F3 : 420. 1020. Found : 420. 1028.

EXAMPLE 102 Synthesis of 1- di (4-chlorophenyl) phosphino-2- methoxyl (4-chlorophenyl) phosphinite) ethane An analogous procedure to that for (Et) (EtO) PCH2CH2P (Et) 2 was used for the synthesis of title compound using polymer-bound (4-ClC6H5) PCH2CH2P (4-

ClC6H5) 2 (1.2 g,-0.80 mmol/g,-0.96 mmol, prepared as in Example 5) and MeOH (0.27 g, 6.0 mmol). After the solvents were removed from filtrates by vacuum, 132 mg (30% yield) of (MeO) (4-ClC6H5) PCH2CH2P (4-ClC6H5) 2 was obtained. It was >95% pure by I H NMR and GC/MS. 31p NMR (202 MHz, CDC13): 8 124.7 (d, J = 27. 9 Hz),-13. 4 (d, J = 27.9 Hz). 1. NMR (500 MHz, CDC13): 6 7.28-7.12 (m, 12H), 3.45 (d, Jp-H = 13.6 Hz, 3H), 1.93 (m, 2H), 1.66 (m, 2H). 13C (125 MHz, CDC13): 8 139.6,136.2,135.2,135.1,133.9,130.7, 128.8,128.5,56.8,30.5,21.1. HRMS: Calcd. for C2lHlgP2OCl3 : 453.9977.

Found: 453.9951.

EXAMPLE 103 Synthesis of 1- di (2-mesityl) phosphino-2- methoxyl (2-mesityl) phosphinite] ethane The procedure described above was employed except that polymer-bound (2,4,6-Me3C6H2) PCH2CH2P (2,4,6-Me3C6H2) 2 (1.33 g,-0.72 mmol/g, -0.96 mmol, prepared as in Example 5) and MeOH (0. 21 g, 6.0 mmol) were used to prepare the title compound. After the solvents were removed from filtrates by vacuum, 136 mg (30% yield) of (MeO) (2,4,6-Me3C6H2) PCH2CH2P (2,4,6- Me3C6H2) 2 was obtained. It was >95% pure by IH NMR and GC/MS. 3 IP NMR (202 MHz, CDC13): 8 131.6 (d, J= 33.2 Hz),-17.7 (d, J= 33.2 Hz). IHNMR (500 MHz, CDC13): 8 6.75 (m, 6H), 3.47 (d, Jp H= 14.3 Hz, 3H), 2.48-2.19 (m, 31H). 13C (125 MHz, CDC13): 8 132.7,132.6, 129.8,67.9,57.1,28.0,25.6,23.1,21.3,20.7. HRMS: Calcd. for C3oH4oP20 : 478.2554. Found: 478.2553.

EXAMPLE 104 Synthesis of 1- diphenethylphosphino-2- (methoxylphenethyl phosphinite) ethane A similar procedure to those described above was used to prepare the title compound using polymer-bound (PhCH2CH2) PCH2CH2P (CH2CH2Ph) 2 (1.29 g, -0.74 mmol/g,-0.96 mmol, prepared as in Example 5) and MeOH (0.21 g, 6.0 mmol). After the solvents were removed from filtrates by vacuum, 110 mg (26% yield) of (MeO) (PhCH2CH2) PCH2CH2P (CH2CH2Ph) 2 was obtained. It was >95% pure by IH NMR and GC/MS. 31p NMR (202 MHz, CDC13): 8 138.5 (d, J = 21.7 Hz),-23.0 (d, J = 21.9 Hz). IH NMR (500 MHz, CDC13): 6 7.21-7.08 (m, 15H), 3.44 (d, Jp-H = 12.8 Hz, 3H), 2.77-2.64 (m, 6H), 1.91 (m, 2H), 1.67 (m, 6H), 1.51 (m, 2H). 13C (125 MHz, CDC13): 8 142.8,142.5,128.8, 128.3,126.7,126.2,126.0,125.9,57.1,34.5,32.2,30.5,28.2,27.8, 20.3. HRMS: Calcd. for C27H35P20 (M + H) +: 437.2163. Found: 437.2197.

EXAMPLE 105 Synthesis of 1- (diphenylphosphino)-2- (l-propylthio-l-phenylphosphinite) ethane A suspension of polymer-bound (Ph) PCH2CH2P (Ph) 2 (1.0 g, 0.96 mmol, prepared as in Example 5) and CH3CH2CH2SH (0.366 g, 4.8 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess CH3CH2CH2SH. The resulting residue was 117 mg (31 % yield) of (Ph) (CH3CH2CH2S) PCH2CH2P (Ph) 2. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, CDC13): 6 30.0 (d, J = 30. 0 Hz),-11.8 (d, J = 29.9 Hz). IH NMR (500 MHz, CDC13): 6 7.45-7.20 (m, 15H), 2.52 (m, 2H), 2.13 (m, 2H), 1.89 (m, 2H), 1.53 (m, 2H), 0.84 (t, J = 7.34 Hz, 3H). 13C NMR (125 MHz, CDC13): 8 138. 5, 138. 0, 133. 3, 132. 8, 131. 6, 128. 8, 128. 6, 128. 4, 35. 1, 26. 9, 25.1,23.6,13.2. HRMS: Calcd. for C23H26P2S : 396.1230. Found: 396.1217.

EXAMPLE 106 Synthesis of 1- (diisopropylphosphino)-2- (1-propylthio-1-isopropyl phosphinite) ethane A suspension of polymer-bound (i-C3H7) PCH2CH2P (i-C3H7) 2 (1.0 g, 0.92 mmol, prepared as in Example 5) and CH3CH2CH2SH (0.46 g, 6.0 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess CH3CH2CH2SH. The resulting residue was 144 mg (53 % yield) of (i- C3H7) (CH3CH2CH2S) PCH2CH2P (i-C3H7) 2. It was >95% pure by IH NMR and GC/MS. 31P NMR (121 MHz, CDC13): 8 51.5 (d, J = 27.4 Hz), 9.9 (d, J = 27.5 Hz).'H NMR (500 MHz, CDC13): 6 2.54-2.49 (m, 2H), 1.75-1.57 (m, 9H), 1.03 (m, 18H), 0.92 (t, J = 7.35 Hz, 3H). 13C NMR (125 MHz, CDCl3): 8 35.7,27.7, 25.1,23. 3, 19. 8, 19. 0, 18. 9, 18. 8, 13. 1 HRMS : Calcd. for CllH25P2S (M+- C3H7): 251.1152. Found: 251.1153.

EXAMPLE 107 Synthesis of 1- (di-3', 4', 5'-trifluorophenylphosphino)-2- (1-propylthio-3', 4', 5'-trifluorophenylphosphinite) ethane A suspension of polymer-bound (F3H2C6) PCH2CH2P (C6H2F3) 2 (1. 0 g, 0.74 mmol, prepared as in Example 5) and CH3CH, CH2SH (0.46 g, 6.0 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess CH3CH2CH2SH. The resulting residue was 295 mg (71 % yield) of (C6H2F3) (CH3CH2CH2S) PCH2CH2P (C6H2F3) 2. It was >95% pure by IH NMR and GC/MS. 31p NMR (121 MHz, CDC13): 6 31.1 (d, J = 31. 7 Hz),-9.1 (d, J =

31.5 Hz). IH NMR (500 MHz, CDC13): 8 7.12 (m, 2H), 6.87 (m, 4H), 2.57 (m, 2H), 2.01 (m, 2H), 1.76 (m, 2H), 1.54 (m, 2H), 0.86 (t, J = 7. 28 Hz, 3H). 13C NMR (125 MHz, CDC13): 6 152.3,150.3,140.9,139.0,135.2,133.2,116.3, 115.0, 35. 4, 26. 7, 25. 1, 23. 5, 12. 9. HRMS : Calcd. for C23HI7P2F9S : 558. 0382.

Found: 558.0369.

EXAMPLE 108 Synthesis of 1- (diisopropylphosphino)-2- (1-diethylamino-1-isopropyl phosphinite) ethane A polymer-bound (i-C3H7) PCH2CH2P (i-C3H7) 2 (1.0 g, 0.92 mmol, prepared as in Example 5) resin was quickly washed with HC1 solution (1.0 M in Et20,10 mL) over a period of 1.0 min. and then removal of all the solution by filtration. The resulting resin and Et2NH (0.45 g, 6.2 mmol) in THF (10 mL) was refluxed overnight before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess Et2NH.

The resulting residue was 120 mg (45 % yield) of (i-C3H7) (Et2N) PCH2CH2P (I- C3H7) 2. It was >95% pure by IH NMR and GC/MS. 31p NMR (202 MHz, CDC13): 6 47.0 (d, J = 40.3 Hz), 10.4 (d, J = 40.3 Hz). IH NMR (500 MHz, CDC13): 8 1.98-1.95 (m, 2H), 1.88 (m, 1H), 1.78 (m, 1H), 1.70 (m, 4H), 1.50 (m, 2H), 1.19-1.12 (m, 9H), 1.06-0.96 (m, 16H). 13C NMR (125 MHz, CDCl3): 8 26.5,23.5,23.1,19.8,18.7,15.3,14.8,13.1. HRMS: Calcd. for C11H27P202 (M02+-Et2N + H+): 253.1486. Found: 253.1411.

EXAMPLE 109 Synthesis of 1- (di-o-tolylphosphino)-2- (o-tolyl-chlorophosphinite) ethane A suspension of polymer-bound (o-MeH4C6) PCH2CH2P (o-MeC6H4) 2 (1.5 g, 0.81 mm/g, 1.2 mmol, prepared as in Example 5) and PCl3 (0.82 g, 6.0 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 5 mL). The filtrate was dried in vacuo to remove the solvent and excess PCl3. The resulting residue was 365 mg (75 % yield) of (o-MeH4C6) (Cl) PCH2CH2P (o-MeC6H4) 2. It was >95% pure by IH NMR and GC/MS. 31p NMR (121 MHz, C6D6): 8 89.5 (d, J = 39.7 Hz),-33.0 (d, J = 39.7 Hz). 1H NMR (500 MHz, CDC13): 8 7.4-6.7 (m, 12H), 2.17 (s, 6H), 2.10 (s, 3H), 1.97 (m, 4H). 13C NMR (125 MHz, C6D6): 129. 0,127.6,127.1, 125.4, 125. 2, 66. 4, 30. 2, 24. 4, 19. 8. HRMS : Calcd. for C23H26P20 (MO+-Cl + H): 380.1459. Found: 380.1513.

EXAMPLE 110 Synthesis of 1- (di-3,5-difluorophenylphosphino)-2- (3,5-difluorophenyl-chlorophosphinite) ethane A suspension of polymer-bound (C6H3F2) PCH2CH2P (C6H3F2) 2 (6.0 g, 0.77 mm/g, 4.6 mmol, prepared as in Example 5) and PC13 (5.0 g, 36.4 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 5 mL) and hexane (2 X 10 mL). The combined filtrates were dried in vacuo to remove the solvent and excess PC13.

The resulting residue was extracted with hexane (3 X 30 mL). The concentration of the extracts afforded 1.58 g (74%) of the title compound (C6H3F2) (Cl) PCH2CH2P (C6H3F2) 2. It was >95% pure by 1H NMR and GC/MS.

31p NMR (202 MHz, CDC13): 6 90.8 (d, J = 29.8 Hz),-9.2 (d, J = 29.9 Hz). 1H NMR (500 MHz, CDC13): 8 7.03 (m, 3H), 6.76 (m, 6H), 2.02 (m, 4H), 1.97.13C NMR (125 MHz, C6D6): 6 164.1,162.0,141.9,140.9,115.1,113.4,106.3,105.1, 32.4,22.0. HRMS: Calcd. for C2oHl3F6P2Cl: 464.0085. Found: 464.0075.

EXAMPLE 111 Synthesis of 1- (di-2-thienylphosphino)-2- (2-thienylchlorophosphinite) ethane A suspension of polymer-bound (2-C4H3S) PCH2CH2P (2-C4H3S) 2 (1.5 g, 0.93 mm/g, 1.4 mmol, prepared as in Example 5) and PC13 (1.0 g, 7.3 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 5 mL) and hexane (2 X 10 mL). The combined filtrates were dried in vacuo to remove the solvent and excess PCl3.

The resulting residue was 300 mg (57%) of the title compound (2-C4H3S) (C1) PCH2CH2P (2-C4H3S) 2. It was >95% pure by H NMR and GC/MS. 31P NMR (202 MHz, CDC13): 6 76.7 (d, J = 38.3 Hz),-38. 3 (d, J = 38. 3 Hz). IH NMR (500 MHz, CDC13): 6 7.63 (d, J = 4.97 Hz, 1H), 7.48 (d, J = 4.89 Hz, 1H), 7.44-7.42 (m, 1H), 7.30-7.28 (m, 2H), 7.02-6.98 (m, 4H), 2.27-2.16 (m, 4H). ¹³C NMR(125 MHz, C6D6): # 139.5, 138.3, 137.0, 136.8, 135.5,(125 MHz, C6D6): # 139.5, 138.3, 137.0, 136.8, 135.5, 133.8, 132.8,127.8,33.9,26.9. HRMS: Calcd. for Ci4HS3P2 (M+-Cl + H): 339.9733. Found: 339.9742.

EXAMPLE 112 Synthesis of (C6H50) (Cl) PCH2CH2P (OC6H5) 2 A solution of PhOH (3.0 g, 31.9 mmol) in THF (30 mL) was treated with n-BuLi (1.6 M solution in THF, 16 mmol) at room temperature over a period of 5 min. and stirred for 2 h before 1.0 g of polymer-bound (Cl) PCH2CH2P (Cl) 2 (1.0 g, 0.94 mm/g, 0.94 mmol, prepared as in Example 5) was added. The resulting suspension was stirred at room temperature for 2 h before the excess

PhOH and PhOLi were filtered off, and the resin was washed with THF (3 X 20 mL), hexane (3 X 20 mL). The resulting resin was dried in vacuo overnight.

A suspension of the resin above (0.61 g, 0.82 mm/g, 0.50 mmol) and PC13 (0.62 g, 4.5 mmol) in THF (10 mL) was stirred overnight at room temperature before the resin was filtered off and washed with THF (2 X 5 mL) and hexane (2 X 10 mL).

The combined filtrates were dried in vacuo to remove the solvent and excess PC13.

The resulting residue was 133 mg (56%) of the title compound (C6H50) (Cl) PCH2CH2P (OC6H5) 2. It was >95% pure by 1H NMR and GC/MS.

31p NMR (121 MHz, C6D6): 5 199.5 (d, J = 16.8 Hz), 178.9 (d, J = 16.8 Hz). 1H NMR (500 MHz, CDC13): 8 7.25-6.93 (m, 15H), 2.40 (m, 2H), 2.16 (m, 2H).

13C NMR (125 MHz, CDC13) : 8 155. 4, 155. 0, 129. 9, 129. 8, 124. 7, 123. 8, 119. 9, 119.4,31.1,27.7. HRMS: Calcd. forCHi402P2Cl (M+-OPh): 311.0158.

Found: 311.0117.

EXAMPLE 113 Synthesis of 1- (di-3,5-difluorophenylphosphino)-2- (3,5-difluorophenyl-phenylphosphinite) ethane A solution of 700 mg (1.5 mmol) of (C6H3F2) (Cl) PCH2CH2P (C6H3F2) 2 in 20 mL of THF was treated with PhMgCl (3 M solution in THF, 1.7 mmol, prepared as in Example 5) at room temperature over a period of 5 min. and stirred for 1 h before the reaction was quenched with MeOH (2 mL). The resulting mixture was dissolved in a mixture of H20 (2 mL)/THF (10 ml), and extracted with hexane (3 X 20 mL). After separation, the hexane extracts were dried over MgSO4, filtered, and the hexane and THF removed from the filtrate by vacuum, to afford 450 mg (59%) of (C6H3F2) (Ph) PCH2CH2P (C6H3F2) 2. It was >95% pure by IH NMR and GC/MS. 31P NMR (202 MHz, C6D6): 8-8.4 (d, J = 38.8 Hz),- 10.3 (d, J = 38.9 Hz). 1H NMR (500 MHz, C6D6): 6 7.00-61.3 (m, 14H), 1.66-1.57 (m, 3H), 1.16 (m, 1H). 13C NMR (125 MHz, C6D6): 8 164.6,162.6,136.5,133.8,129.4,128.9,128.6,128.4,115.6,114.9, 105.4,104.7.

24.2,23.9. HRMS: Calcd. for C26HlgF6P2: 506.0788. Found: 506.0794.

EXAMPLES 114-116 Synthesis of Diphosphine Ligand Array Library A solution of 700 mg (1.5 mmol) of (C6H3F2) (Cl) PCH2CH2P (C6H3F2) 2 in mixture of 15 mL of THF and 5 mL of THF-dg was divided into 34 NMR tubes (0.6 mL/tube) in the dry-box. Each NMR tube above was treated with only one RgMgX (1-1.2 eq) at room temperature before the NMR tube was sealed. It was >95% pure by 3 1 P NMR and GC/MS. This was repeated using 1-(di-(2-thienyl phosphino))-2-chloro-2-thienylphosphinoethane and 1- (di- (o-tolyl phosphino))-2-

chloro-o-tolylphosphinoethane. The scheme and results where x=Cl are shown in Tables 6A-8A.

TABLE 6A MW MW Ex. R 31P NMR m J- (calc.) (found) 114-AH-6.8-61.9 26. 5 430- 114-B phenyl-7. 9-9. 8 38. 7 506 507.6 114-C o-tolyl-7.6-20.5 39. 9 520 521.7 114-D m-tolyl-7.5-9.6 38. 8 520 521.7 114-E p-tolyl-7.7-10.6 38. 3 520 521.7 114-F 4- (t-butyl) phenyl-7. 6-11. 1 38.4 562 563.8 114-G mesityl-7. 8-19. 0 45. 2 548 549.8 114-H 2, 5-dimethylphenyl-7.7-17.7 44. 9 534 535.7 114-I 3-methyl-4-fluorophenyl-7.7-10.7 40. 0 538 539. 7 114-J 3,4,5-trifluorophenyl-7.6-7.9 39. 9 560 561.7 114-K methyl-7.8-26.3 29. 9 444 445.5 114-L ethyl-7.9-11.8 31. 5 458 459.5 114-M n-propyl-8.0-16.8 31. 5 472 473.7 114-N cyclopentyl-4.1-7.8 30. 8 498 499.6 114-O n-heptyl-7.9-16.1 31. 4 500 501.6 114-P cyclohexyl-3. 7-7. 8 34. 2 512 5137 114-Q phenylmethyl-7.5-11.2 33. 4 520 521.6 114-R 2-butyl-2.6-7.7 34. 2 486 487.6 (-2.9) (-7.8) (34.6) 114-S t-butyl-11.2-7.7 38. 6 486 487.6 114-T n-pentadecyl-7.8-16.1 31. 3 640 642.1 MW MW Ex. Rg 31PN Rppm jp-p (calc.) (found) 114-U 3, 5-difluorophenyl-8. 1--542 543.8 114-V i-propyl-7. 6 0. 9 33. 4 472 473.6 114-W 3-chloro-4-fluorophenyl-8. 9-11. 3 40. 4 558. 5 559.7 114-X phenethyl-7.6-15.2 31. 7 534 535.7 114-Y i-butyl-7.7-19.9 31. 6 486 487.6 114-Z 2-methyl-2-phenylpropyl-7. 7-23. 7 32. 8 562 563.8 114-AA n-decyl-7. 8-16. 0 31. 2 570 571.9 114-BB 3, 4-dimethoxyphenyl-7.5-9.0 38. 4 566 567.8 114-CC 2-methoxy-4-fluoro- -7.5 -16.3 39.6 554 555.7 phenyl 114-DD 2-methoxy-7.7-11.0 38. 6 598 599.9 114-EE 4-phenoxyphenyl -7.3 -15.6 38.8 536 537.7 114-FF allyl-7.5-17.2 33. 4 470 471.5 114-GG thiophenyl-7. 8 34. 6 34.4 538 539.6 114-HH phenoxy-7.5 118.9 28. 8 522 523.6 TABLE 7A

MW MW Ex. Rg 31P NMR rpm JP-P (calc.) (found) 115-AH-52.2-34.5 18.5 364 365.4 115-B phenyl-22.4-33 34.8 440 441.6 115-C o-tolyl-33. 2--454 455.6 115-D m-tolyl-22.5.32.9 34.8 454 455.6 115-E p-tolyl-23.4-33.1 34.5 454 455.6 115-F 4- (t-butyl) phenyl-24.1-32.8 34.4 496 497.8 115-G mesityl-29.5-32.6 44.2 482 483.7 115-H 2, 5-dimethylphenyl-28.2-32.7 36.4 468 469.7 115-I 3-methyl-4-fluorophenyl -23.7 -33.1 35.2 472 473.7 MW MW Ex. R 31P NMR m J- (calc.) (found) 115-J 3, 4, 5-trifluorophenyl-20.2-33.4 37. 4 494 495.7 115-K methyl-43. 2-33. 6 26. 4 378 379.5 115-L ethyl-29.4-33.4 27. 8 392 393.5 115-M n-propyl-34. 7. 33. 4 28. 1 406 407.6 115-N cyclopentyl-21. 9-33. 2 26. 3 432 433.6 115-O n-heptyl-34.1-33.4 27. 8 434 435.7 115-P cyclohexyl-23.2-33.1 30. 8 446 447.7 115-Q phenylmethyl-26.9-33.3 30. 3 454 487.7 (MO 115-R 2-butyl-22. 2-33. 0 30. 7 420 421.6 (-21.7) (-32.9) (30.5) 115-S t-butyl 9.9-32.6 345 420 421.6 115-T n-pentadecyl-34.2-33.4 40. 6 574 576.1 115-U 3, 5-phenyl-20.1-33.2 37. 0 476 477.6 115-V i-propyl-18. 1-33. 1 29. 8 406 407.5 115-W 3-chloro-4-fluorophenyl-22.7-33.1 35. 2 493 493.7 115-X phenethyl-33. 4-33. 1 28.4 468 469.7 115-Y i-butyl-38.7-33.3 28. 6 420 421.6 115-Z 2-methyl-2-phenylpropyl-43. 4-33. 2 30. 8 496 497.8 115-AA n-decyl-34.1-33.4 27. 8 504 505.8 115-BB 3, 4-dimethoxyphenyl-22.2-32.9 34. 4 500 501.8 115-CC 2-methoxy-4-fluoro--31.5-33.2 35. 4 488 489.7 phenyl 115-DD 4-phenoxyphenyl-23.9-33.0 34. 9 532 533.8 115-EE 2-methoxy-31.5-33.1 34. 1 470 471.7 115-FF allyl-34.1-33.3 29. 8 404 405.5 115-GG thiophenyl 21.2-33.4 35. 5 472 473.6 115-HH phenoxy 114. 6-33. 5 27. 0 456 457.6 TABLE 8A MW MW Ex Rg 31 P NMR ppm Jp-p (calc.) (found) 116-A H-73.5-39.4 27.5 340 342 116-B phenyl-25.0-38.3 37.4 416 417.4 116-C o-tolyl-36.0-38.5 39.0 430 431.4 116-D m-tolyl-25.1-38.3 37.4 430 431.4 116-E p-tolyl-25.8-38.3 37.2 430 431.5 116-F 4- (t-butyl) phenyl-26. 3-38. 3 37.4 472 473.5 116-G mesityl-26.1-38.2 43.8 459 459.5 116-H 43.8 444 445.5 116-I 3-methyl-4-fluorophenyl-26.0 38.4 38.8 448 449.5 116-J 6 39.2 470 471.5 116-K methyl-40.5-38.4 32.2 354 387.3 (MO ? +) 116-L ethyl-26. 1-38.4 32.4 368 401.5 (MA ? +) 116-M n-propyl-31.2-38.4 32.6 382 415.4 116-N cyclopentyl-18.9-38.3 31.5 408 441.4 (mu+) 116-O n-heptyl-30.5-38.4 32.4 410 411.4 116-P cyclohexyl-18.8-38.3 33.0 422 423.4 116-Q phenylmethyl-24.7-38.2 33.4 430 463.5 (M02+) 116-R 2 396 429.4 (-17.6) (-38.2) (33.2) (MO ? +) 116-S t-butyl-2.2-38.1 37.2 396 429.4 (MOv+) 116-T n-pentadecyl-30.6-38.5 32.5 550 551.8 116-U 5 38.8 452 453.4 116-V i-propyl-14.1-38.3 32.8 382 383.3 116-W 3-chloro-4-fluorophenyl-25.4-38.5 38.9 469 469.4 116-X phenethyl-30. 1-38.4 32.7 444 445.5 MW MW Ex Ro 31 P NMR ppm 1 JP-P (calc.) (found) t, I 116-Y i-butyl-34.4-38.4 32.7 396 397.4 116-Z 2-methyl-2-phenylpropyl-38.8-38.5 33.7 472 505.7 (MO ? +) 116-AA n-decyl-30.5-38.4 32.4 480 481.6 116-BB 3, 4-dimethoxyphenyl-24.6-38.2 37.4 476 477.5 116-CC 2-r. mttioxy-4-fluoro--31. 1-38.3 38.0 464 465.5 phenyl 116-DD 4-phenoxyphenyl-26. 2-38. 3 37.6 508 509.6 116-EE 2-methoxy -31.1-38.1 37.2 446 447.4 116-FF allyl-30.9-38.4 33.5 380 413.3 (MO ? +) 116-GG thiophenyl 37. 3 448 482.4 ! (MO ? +) phenoxy 110. 3 36.4 432 431. 0

Synthesis of Polymer-Bound Diphosphine Monoxide Ligands EXAMPLE 117 Polymer-Bound (Me2CH) P (O) CH2CH2P (CHMe2) 2 A solution of 160 mg (0.68 mmol) of (Me2CH) PH (O) CH2CH2P (CHMe2) 2 from Example 26 and 1.0 mg (0.015 mmol) of NaOEt in 10 mL of THF was stirred at room temperature over a period of 20 min before formypolystyrene (2% DVB, 0.90 g, 0.46 mmol/g, 0.41 mmol) was added to the reaction mixture. The resulting suspension was stirred overnight. After the solution was filtered off. resin was washed with THF (3 X 20 mL), hexane (3 X 20 mL). The resulting resin was dried in vacuo overnight to afford polymer-bound (Me2CH) PH (O) CH2CH2P (CHMe2) 2.3lP NMR (122 MHz, CDC13): 6 53.3 (s), 10.5 (s) ppm. ¹³C NMR (75 MHz, CDCl3): # 31.5,25.5,22.9 (d, Jp-c = 55.6 Hz), 20.0,18.9,15.7,14.1.

EXAMPLE 118 Polymer-Bound (Ph) PCH2CH2PPh (O) (C6H2Me3) A solution of 150 mg (0.614 mmol) of PhPH (O) (2,4,6-C6HoMe3) from Example 61 and 1.0 mg (0.01 mmol) of NaOtBu in 10 mL of THF was stirred at room temperature over a period of 10 min before polymer-bound PhPCH=CH2 (2% DVB, 0.5 g, 0.938 mmol/g, 0.469 mmol, from Example 52-S) was added to the reaction solution. The resulting suspension was refluxed overnight. After the solution was filtered off, resin was washed with THF (3 X 20 mL), Me2CHOH

(2 X 5 mL), hexane (3 X 20 mL). The resulting resin was dried in vacuo overnight to afford polymer-bound (Ph) PCH2CH2PPh (O) (C6H2Me3). 31p NMR (122 MHz, CDC13): 6 62.4 (s), 37.8 (s) ppm.

EXAMPLE 119 Synthesis of PhPH (O) CH2CH2PPh (O) (C6H2Me3) A suspension of polymer-bound (Ph) PCH2CH2PPh (O) (C6H2Me3) above (0.5 g,-0.469 mmol) and H20 (0.5g, 27.8 mmol) in 10 mL of THF was refluxed overnight. After the resin was filtered off and washed with THF (10 mL), the filtrates were dried in vacuo to remove the solvents and excess H20. The resulting residue was 50 mg (28 % yield) of PhPH (O) CH2CH2PPh (O) (C6H2Me3).

It was >95% pure by 1H NMR and GC/MS. 31p NMR (202 MHz, CDCl3, IH-decoupled): 8 39.2 (d, J = 52.5 Hz), 28.2 (d, J = 52.3 Hz); 39.0 (d, J = 50.9 Hz), 28.0 (d, J = 50.7 Hz). 31P NMR (121 MHz, CDC13, IH-coupled): 8 39.3 (d, Jp p = 48.5 Hz), 28.1 (d, Jp-H = 474.7 Hz); 39.0 (d, Jp-p = 48.8 Hz), 28.0 (d, JP-H = 474.7 Hz). IH NMR (500 MHz, CDCl3): 8 7.51 (d, Jp-H = 472.9 Hz), 7.48 (d, Jp-H = 473.6 Hz), 7.65-7.30 (m, 10H), 6.82 (d, J = 3.31 Hz, 1H), 6.78 (d, J = 3.29 Hz, 1H), 2.55 (m, 4H), 2.33 (s), 2.28 (s), 2.22 (s), 2.20 (s). 13C NMR (125 MHz, CDC13): 6 143.3,142.2,135.5,132.9,131.7,131.5,130.1, 130.0,129.2,129.0,124.0,123.0,23.6,21.1.

Synthesis of C 1 and C2-Diphosphorus-related Ligands EXAMPLE 120 Synthesis of polymer-bound 1- (2,3,4,5-tetraethylphospholyl)- 2-chlorophosphinoethane Chloromethylpolystyrene-divinylbenzene (50 g, 44.5 mmol, 2% DVB) was added to a solution of t-butylamine (69.6 g, 950 mmol) in THF (700 mL), and the reaction mixture was refluxed overnight before the resin was filtered, washed with H20 (500 mL), THF (500 mL), hexane (500 mL), H20 (500 mL), and Et2O (500 mL). The resulting resin was dried in vacuo, and then added to THF (700 mL). The mixture was cooled to 0 °C and treated dropwise with n- butyllithium (64 mmol, 1.6 M solution in pentane) over a period of 2 h before warmed to room temperature and stirred overnight. After filtration, the resin was washed with hexane (400 mL), THF (400 mL), Et20 (400 mL). The resin was slowly added to a solution ofCl2PCH2CH2PCl2 (37.0 g, 159.6 mmol) in THF (800 mL) at room temperature, and the resulting mixture was stirred overnight before filtration and washing with THF (2 X 400 mL), hexane (2 X 400 mL), CH2Cl2 (2 X 400 mL), hexane (2 X 400 mL). The resin was added to CH2Cl2 (500 mL), and then at room temperature treated with a mixture of CH2C12 (50

mL) and Cp2ZrC4Et4 (17.2 g, 45 mmol) generated from the reaction of Cp2ZrCl2, n-butyllithium, and EtC-CEt. After the mixture was stirred for 4 h, the solvents were filtered off and the resulting resin was washed with CH2C12 (3 X 500 mL), THF (3 X 500 mL), and hexane (3 X 500 mL), dried in vacuo to give 50 g (96% yield with respect to the starting Merrifield resin, which was determined using N, P, and Cl elemental analysis) of the title polymer-bound compound. 31 P NMR (122 MHz, C6D6): d 154.2,1.3.