Haloaromatic compounds, including especially chloroaromatic compounds, are intermediates which can be used variously in the chemical industry and which serve as preliminary products for the production of agricultural intermediates, pharmaceuticals, colourings, materials, etc.. Vinyl halides are also important intermediates which are used as starting materials for polymers and in the production of the above- mentioned products.

Catalysts which are frequently employed for the functionalisation of haloaromatic compounds or vinyl halides to aromatic olefins or dienes (Heck reaction, Stille reaction), biaryls (Suzuki reaction), alkynes (Sonogashira reaction), carboxylic acid derivatives (Heck carbonylation), amines (Buchwald-Hartwig reaction) are palladium catalysts and nickel catalysts. Palladium catalysts are generally advantageous, owing to the wide applicability of coupling substrates with in some cases good catalytic activities, while nickel catalysts have advantages in the field of the reaction of chloroaromatic compounds and vinyl chlorides. Moreover, nickel is more readily available than palladium.

Palladium and nickel catalysts used within the scope of the activation and further improvement of haloaromatic compounds are both palladium (II) and/or nickel (II) complexes as well as palladium zu and/or nickel (0)

complexes, although it is known that palladium (0) and nickel (0) compounds are the actual catalysts of the reaction. In particular, according to information in the literature, coordinatively unsaturated 14-and 16-electron palladium (0) and nickel (0) complexes stabilised with donor ligands such as phosphanes are formulated as the active species.

When iodides are used as starting materials in coupling reactions it is also possible to dispense with phosphane ligands. However, aryl iodides and vinyl iodides are starting materials which are scarcely available and therefore very expensive, and their reaction additionally yields stoichiometric amounts of iodine salt waste products. If other starting materials are used in the Heck reaction, such as aryl bromides or aryl chlorides, the addition of stabilising and activating ligands is necessary if catalytically effective reaction of the starting materials is to be possible.

The catalyst systems described for olefinations, alkynylations, carbonylations, arylations, aminations and similar reactions frequently have satisfactory catalytic turnover numbers (TON) only with uneconomical starting materials such as iodoaromatic compounds and activated bromoaromatic compounds. Otherwise, in the case of deactivated bromoaromatic compounds and, especially, in the case of chloroaromatic compounds, large amounts of catalyst - usually more than 1 mol. %-must generally be added in order to achieve industrially usable yields (> 90 %).

Moreover, owing to the complexity of the reaction mixtures, simple recycling of the catalyst is not possible, so that recovery of the catalyst also gives rise to high costs, which generally stand in the way of industrial implementation. Furthermore, it is undesirable to work with large amounts of catalyst, especially when preparing active ingredients or preliminary products for active ingredients,

because catalyst residues otherwise remain in the product in this case.

More recent active catalyst systems are based on cyclopalladated phosphanes (W. A. Herrmann, C. Brosser, K. Ofele, C. -P. Reisinger, T. Priermeier, M. Beller, H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int.

Ed. Engl. 1995,34, 1844) or mixtures of sterically demanding arylphosphanes (J. P. Wolfe, S. L. Buchwald, Angew. Chem. 1999, 111, 2570; Angew. Chem. Int. Ed. Engl.

1999,38, 2413) or tri-tert. -butylphosphane (A. F. Littke, G. C. Fu, Angew. Chem. 1998, 110, 3586; Angew. Chem. Int.

Ed. Engl. 1998,37, 3387) with palladium salts or palladium complexes.

However, chloroaromatic compounds can generally not be activated in an industrially satisfactory manner even using these catalysts. Accordingly, in order to achieve high yields, comparatively large amounts of catalyst must be used. Therefore, despite all the further developments which have been made to catalysts in recent years, only a small number of industrial reactions of the arylation, carbonylation, olefination, etc. of chloroaromatic compounds have hitherto become known.

For the mentioned reasons, the object underlying the present invention was to provide novel ligands and catalysts which are suitable for large-scale applications, are readily accessible and convert chloro-and bromo- aromatic compounds as well as corresponding vinyl compounds to the respective coupling products in high yield and with high purity, with high catalyst productivity.

This object is achieved according to the invention by novel phosphane ligands of formula (I)

wherein X independently of Y represents a nitrogen atom or a C-R2 group and Y independently of X represents a nitrogen atom or a C-R9 group, Ri for each of the two R1 groups independently of the other represents a radical selected from the group Cl-C24-alkyl, C3-C20-cycloalkyl, which includes especially both monocyclic and also bi-and tri-cyclic cycloalkyl radicals, C5-C14-aryl, which includes especially the phenyl, naphthyl, fluorenyl radical, C2-C13-heteroaryl, wherein the number of hetero atoms, selected from the group N, 0, S, may be from 1 to 2, wherein the two radicals R1 may also be linked to one another, there preferably being formed a 4-to 8- membered saturated, unsaturated or aromatic ring.

The above-mentioned radicals R1 may themselves each be mono-or poly-substituted. These substituents, independently of one another, may be hydrogen, C1-C20- alkyl, C2-C20-alkenyl, C3-C8-cycloalkyl, C2-C9-hetero- alkyl, Cs-Clo-aryl, C2-Cg-heteroaryl, wherein the number of hetero atoms, especially from the group N,

0, S, may be from 1 to 4, C1-C20-alkoxy, preferably Cl-Clo-alkoxy, particularly preferably OMe, Cl-Clo-halo- alkyl, preferably trifluoromethyl, hydroxy, secondary, tertiary amino groups of the forms NH-(C1-C20-alkyl), NH- (C5-Cio-aryl), N (C1-C20-alkyl) 2, N (C1-C20- alkyl) (C5-C10-aryl), N (C5-C10-aryl) 2, N (C1-C20- alkyl/C5-Clo-aryl3) 3+, NH-CO-C1-C20-alkyl, NH-CO-C5-Clo- aryl, carboxylato of the forms COOH and COOQ (wherein Q represents either a monovalent cation or C1-C8- alkyl), Cl-C6-acyloxy, sulfinato, sulfonato of the forms SO3H and SO3Q (wherein Q represents either a monovalent cation, C1-C20-alkyl or C5-Clo-aryl), tri- Cl-C6-alkylsilyl, especially SiMe3, wherein two of the mentioned substituents may also be bridged with one another, there preferably being formed a 4-to 8-membered ring which can be further substituted preferably by linear or branched Cl-Clo- alkyl, C6-aryl, benzyl, Cl-Clo-alkoxy, hydroxy or benzyloxy groups.

R2-R3 represent a hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl, N- (alkyl) 2, O-(aryl), NH-(aryl), N-(alkyl) (aryl), O-CO- alkyl, 0-CO-aryl, F, Si (alkyl) 3, CF3, CN, C02H, COH, SO3H, CONH2, CONH (alkyl), CON (alkyl) 2, S02 (alkyl), SO (alkyl), SO (aryl), SO2 (aryl), S03 (alkyl), SO3 (aryl), S-alkyl, S-aryl, NH-CO (alkyl), C02 (alkyl), CONH2, CO (alkyl), NHCOH, NHCO2 (alkyl), CO (aryl), C02aryl) radical, wherein two or more adjacent radicals, each independently of the other (s), may also be linked to one another so that a condensed ring system is present and wherein in R2 to R9

alkyl represents a hydrocarbon radical having from 1 to 20 carbon atoms which may in each case be linear or branched, alkenyl represents a mono-or poly- unsaturated hydrocarbon radical having from 2 to 20 carbon atoms which may in each case be linear or branched, and cycloalkyl represents a hydrocarbon having from 3 to 20 carbon atoms, wherein the alkyl, alkenyl and cycloalkyl groups may also carry further substituents as defined for R1. Preferred substituents in this connection are selected from the group Br, Cl, F, (Cl-Cl2)-alkyl, O-(Cl-Cl2)-alkyl, phenyl, 0-phenyl, NH ((Cl-Cl2)-alkyl), N ((Cl-Cl2)-alkyl) 2, and aryl represents a 5-to 14-membered aromatic radical in which from one to four carbon atoms may also be replaced by hetero atoms from the group nitrogen, oxygen and sulfur so that a 5-to 14-membered hetero- aromatic radical is present and wherein the aryl or heteroaryl radical may carry further substituents as defined for R1, preferred substituents being selected from the group Br, Cl, F, (Cl-Cl2)-alkyl, 0- (Cl-Cl2)- alkyl, phenyl, 0-phenyl, NH2, NH ( (Cl-Cl2)-alkyl), N ((Cl-Cl2)-alkyl) 2- The mentioned alkyl radicals have preferably from 1 to 10 carbon atoms, particularly preferably from 1 to 5. The alkenyl radicals have preferably from 2 to 10 carbon atoms, particularly preferably from 2 to 5. The cycloalkyl radicals have preferably from 3 to 8 carbon atoms. The aryl radicals have preferably from 6 to 10 carbon atoms, the heteroaryl radicals from 4 to 9.

Preference is given to ligands wherein X is CR2 and Y is CR9, yielding compounds of formula (II)

(II) wherein the radicals R1 to R9 are as defined above. In a further preferred embodiment, X is nitrogen and Y is a CR9 group.

Preferred ligands of formula (I) or (II) carry at least one radical R1 selected from the group consisting of phenyl, Cl-Clo-alkyl, cyclopentyl, cyclohexyl, cycloheptyl, 1- adamantyl, 2-adamantyl, 5H-dibenzophospholyl, 9-phospha- bicyclo [3.3. 1]nonanyl, 9-phosphabicyclo [4. 2. 1] nonanyl radicals. Examples of preferred Cl-Clo-alkyl radicals are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl- propyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2- methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethyl- propyl, n-hexyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl- pentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethyl- butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethyl- butyl, 1-ethylbutyl, 2-ethylbutyl, 1,1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-l-methylpropyl, n-heptyl, n- octyl, n-nonyl, n-decyl, particular preference being given especially to the isopropyl radical and the tert.-butyl radical.

Preferred radicals R2 to R9 are selected from the group hydrogen, Cl-Clo-alkyl, C2-Clo-alkenyl, Cl-Clo-haloalkyl, C3-C8-cycloalkyl, C6-Clo-aryl, which includes especially

also phenyl, naphthyl, fluorenyl, and C2-C6-heteroaryl, wherein from 1 to 3 nitrogen atoms or an oxygen or sulfur atom may be present as hetero atom, and wherein two adjacent radicals R2 to R9 may be bridged with one another, there preferably being formed a 4-to 8- membered, preferably aromatic ring.

The ligands according to the invention can be prepared by reacting the corresponding phenylpyrrole derivative in the presence of a strong base, such as, for example, an alkyl- lithium compound, and subsequently adding a halophosphane, in accordance with the following reaction scheme, which is given by way of example According to the invention, the novel phosphane ligands are used as catalysts in combination with transition metal complexes or transition metal salts of sub-group VIII of the periodic system of the elements, such as, for example, palladium, nickel, platinum, rhodium, iridium, ruthenium, cobalt. The ligands according to the invention can generally be added in situ to corresponding transition metal precursor compounds and accordingly used for catalytic applications. However, it may occasionally be advantageous for specific mono-, di-, tri-or tetra- phosphane complexes of the mentioned transition metals to be prepared first and subsequently used for catalysis

reactions. The catalytic activity can thereby be increased further in some catalyst systems.

As transition metal compounds there are preferably used palladium or nickel compounds and particularly preferably palladium compounds.

The ligands according to the invention are generally added in situ preferably to nickel (II) or palladium (II) salts or to nickel (II), palladium (II) or nickel (0) or palladium (0) complexes. Preferred palladium complexes are, for example, palladium (II) acetate, palladium (II) chloride, palladium (II) bromide, lithium tetrachloropalladate (II), palladium (II) acetylacetonate, palladium (0)-dibenzylidene- acetone complexes, palladium (0) tetrakis (triphenyl- phosphane), palladium (0) bis (tri-o-tolylphosphane), palladium (II) propionate, palladium (II) bis (triphenyl- phosphane) dichloride, palladium (0) diallyl ether complexes, palladium (II) nitrate, palladium (II) chloride bis (acetonitrile), palladium (II) chloride bis (benzo- nitrile).

In catalytic applications, the phosphane ligand is generally used in excess relative to the transition metal. The ratio of transition metal to ligand is preferably from 1: 1 to 1: 1000. Ratios of transition metal to ligand of from 1: 1 to 1: 100 are particularly preferred. The exact transition metal/ligand ratio to be used depends on the concrete application, but also on the amount of catalyst used. Accordingly, it is generally customary to use low transition metal/ligand ratios at very low transition metal concentrations (< 0.01 mol. %) than at transition metal concentrations of from 0.5 to 0.01 mol. % transition metal.

The catalysts are preferably used at temperatures of from 20 to 200°C ; in many cases, it has proved advantageous to work at temperatures of from 30 to 180°C, preferably from

40 to 160°C. The ligands can also be used without any loss of activity in reactions under pressure, reactions usually being carried out only up to a pressure of 100 bar, but preferably in the range of from normal pressure to 60 bar.

When carrying out catalytic reactions using ligands of formula (I), high turnover rates (TON) can be achieved with a low catalyst concentration. The transition metal is preferably used in a ratio of from 5 mol. % to 0. 001 mol. %, particularly preferably from 0.5 mol. % to 0.01 mol. %, relative to the substrate.

The phosphane ligands prepared in accordance with the invention have proved suitable especially as the ligand component for the catalytic preparation of arylated olefins (Heck reactions), biaryls (Suzuki reactions), a-aryl ketones and amines from aryl halides or vinyl halides.

However, it is obvious to the person skilled in the art that the novel catalyst systems can also be used to catalyse other transition-metal-catalysed reactions, such as metathesis or hydrogenations of double bonds or carbonyl compounds, but especially palladium-and nickel-catalysed carbonylations of aryl halides, alkynylations using alkynes (Sonogashira couplings), cross-couplings using organometallic reagents, such as, for example, zinc reagents or tin reagents.

A particular advantage of the ligands according to the invention is the high degree of activity induced by the ligands in the activation of readily available but inert chloroaromatic compounds. The described catalyst and ligand systems can accordingly be used for large-scale purposes.

The phosphanes prepared in accordance with the invention can be used in the preparation of aryl olefins, dienes, diaryls, benzoic acid derivatives, acrylic acid derivatives, arylalkanes, alkynes, amines. The compounds so

prepared are used, for example, as W absorbers, as intermediates for pharmaceuticals and agrochemicals, as ligand precursors for metallocene catalysts, as perfumes, as active ingredients having biological activity and as structural units for polymers.

Implementation Examples: General Reactions of compounds sensitive to air were carried out in an argon-filled glove-box or in standard Schlenk tubes. The solvents tetrahydrofuran (THF), diethyl ether and dichloromethane were degassed and rendered absolute by means of a solvent-drying installation (Innovative Technologies) by filtration through a column packed with activated aluminium oxide. Toluene and pentane were additionally freed of oxygen using a column packed with a copper catalyst.

The Examples which follow serve to explain the invention without limiting it thereto.

Preparation of ligands 1 to 3 (L1 to L3): 10 mmol. of phenylpyrrole are dissolved under argon in 20 ml of absolute hexane. 10 mmol. of TMEDA and 10 mmol. of n-BuLi (1.6 M in hexane) are added at room temperature.

After three hours'heating under reflux, a yellow suspension is obtained. It is cooled to room temperature, and 10 mmol. of Cl-PR12 are slowly added thereto. After reacting for one hour under reflux, hydrolysis is carried out at room temperature using 15 ml of degassed water. The organic phase is transferred to a separating funnel, under argon, with the aid of a cannula. The aqueous phase is extracted twice using 15 ml of hexane each time. The hexane

fractions are likewise transferred to the separating funnel. The combined organic phases are washed with 15 ml of degassed water and dried over degassed sodium sulfate.

The solvents are distilled off and the viscous residue is dissolved in methanol with heating. After one day at room temperature, the mixture is cooled for four hours at 0°C.

The resulting white solid is filtered off and dried in vacuo (purity 90-95 %)- Yields: Pro 2 = PCy2 72 % (31P-NMR :-28. 0 ppm) (L1 ; N-PHOS-Cy) PR12 = PPh2 64 % (31P-NMR : -29. 8 ppm) (L2 ; N-PHOS-Ph) PR12 = PtBu2 40 % (31P-NMR : 3.6 ppm) (L3 ; N-PHOS-tBu) Catalysis Examples 1 to 32: Suzuki couplings 1.25 mmol. of phenylboronic acid and 2.00 mmol. of base are weighed into 2.5 ml glass bottles. These bottles are purged with argon and sealed. All further stock solutions are prepared under argon.

Solution S-1: 147 mmol. of 2-chlorotoluene, 58 mmol. of tetradecane, 155 ml of abs. toluene Solution S-2: 150 mmol. of 4-chloroanisole, 57 mmol. of tetradecane, 154 ml of abs. toluene Solution M-1 : 0.073 mmol. pd of palladium (II) acetate, 49 ml of abs. toluene Solution M-2: 0.065 mmol. Pd of tris-(dibenzylideneacetone)- dipalladium (0), 49 ml of abs. toluene Solution L-1 : 0.04 mmol. of N-PHOS-Cy (L1), 10 abs. toluene Solution L-2: 0.08 mmol. of N-PHOS-tBu (L3), 21 abs. toluene The following solutions are mixed under Ar and stirred for about 1 hour at room temperature (reaction metal precursor with ligand): Ligand Metal precursor M-L-1 5. 0 ml L-1 7. 5 ml M-1 M-L-2 5. 0 ml L-1 7. 5 ml M-2 M-L-3 10. 5 ml L-2 16. 0 ml M-1 M-L-4 10. 5 ml L-2 16. 0 ml M-2

A Vantage synthesizer is used to pipette the following amounts of the resulting solutions into the Vantage vials: 1.1. 25 ml of S-1 (No. 1-8), (No. 17-24) 1.25 ml of S-2 (No. 9-16), (No. 25-32) 2.1. 25 ml of M-L-1 (No. 1-16) or 1.25 ml of M-L-2 (No. 17-32).

Using the Vantage mixing/heating unit, the Vantage vials so filled are heated for 4.0 hours at 110°C (Vantage setting) with shaking (1000 rpm) (heating phase 0.5 h/internal temperature about 120°C).

After the reaction, 1.0 ml of each reaction solution is filtered over silica gel. The solution so obtained is analysed by means of GC. The yields of the individual conversions are summarised in Table 1. Table 1: Summary of the results of Catalysis Examples 1 to 32 No. Starting Lig. Metal precursor Ligand Base Yield material eq. to Eq. to [mmol.] Pd starting Name mol. %Pd Name material 1 1. 0 L-1 Pd (OAc) 2 0.1 2 K3PO4 2 83. 8/89. 1 2 1. 0 L-1 Pd (OAc) 2 0. 1 2 K2CO3 2 78.4/85. 0 3 1.0 L-1 Pd (OAc) 2 0. 1 2 NaOAc 2 9. 1/7.8 4 1. 0 L-1 Pd (OAc) 2 0. 1 2 CS2CO3 2 51. 0/60.8 5 1. 0 L-1 Pd2 (dba) 3 O. 1 2 K3PO4 2 94. 0/89. 8 6 1.0 L-1 Pd2 (dba)3 0.1 2 K2CO3 2 94.8/93. 0 7 1. 0 L-1 Pd2 (dba) 3 O. 1 2 NaOAc 2 34.4/35. 2 8 1.0 L-1 Pd2 (dba) 3 0. 1 2 Cs2CO3 2 57. 7/53. 7 9 1.0 L-1 Pd (OAc)2 0.1 2 K3PO4 2 60. 3/64. 8 10 1. 0 L-1 Pd (OAc) 2 0. 1 2 K2CO3 2 28.0/40. 5 11 1.0 L-1 Pd (OAc)2 0.1 2 NaOAc 2 3.6/3. 7 12 1.0 L-1 Pd (OAc) 2 0. 1 2 Cs2CO3 2 36.3/10. 0 13 1. 0 L-1 Pd2 (dba) 3 O. 1 2 K3PO4 2 84.8/95. 8 14 1.0 L-1 Pd2 (dba)3 0.1 2 K2CO3 2 65.5/68. 2 15 1. 0 L-1 Pd2 (dba) 3 0. 1 2 NaOAc 2 23.5/24. 0 16 1. 0 L-1 Pd2 (dba) 3 0. 1 2 CS2CO3 2 34. 7/27. 2 17 1. 0 L-2 Pd (OAc) 2 0. 1 2 K3PO4 2 61. 4/84. 5 18 1. 0 L-2 Pd (OAc) 2 0. 1 2 K2CO3 2 52.5/50. 1 19 1.0 L-2 Pd (OAc) 2 0. 1 2 NaOAc 2 19. 4/16.5 20 1.0 L-2 Pd (OAc) 2 0. 1 2 CS2C03 2 18. 1/12. 8 21 1. 0 L-2 Pd2 (dba) 3 O. 1 2 K3PO4 2 98.9/96. 1 22 1. 0 L-2 Pd2 (dba) 3 0. 1 2 K2CO3 2 93. 4/91.3 23 1. 0 L-2 Pd2 (dba) 3 0. 1 2 NaOAc 2 17.4/6. 1 24 1. 0 L-2 Pd2 (dba) 3 O. 1 2 CS2CO3 2 36.5/31. 7 25 1.0 L-2 Pd (OAc) 2 0. 1 2 K3PO4 2 83.5/97. 3 26 1. 0 L-2 Pd (OAc) 2 0. 1 2 K2CO3 2 74.1/60. 1 27 1. 0 L-2 Pd (OAc) 2 0. 1 2 NaOAc 2 33.2/39. 4 28 1.0 L-2 Pd (OAc) 2 0. 1 2 CS2CO3 2 69.6/66. 4 29 1.0 L-2 Pd2 (dba) 3 0. 1 2 K3PO4 2 91.5/99. 6 30 1.0 L-2 Pd2 (dba) 3 0. 1 2 K2SO3 2 81.7 No. Starting Lig. Metal precursor Ligand Base Yield material eq. to Eq. to [mmol.] Pd starting Name mol. * Name material 31 1.0 L-2 Pd2 (dba) 3 0. 1 2 NaOAc 2 26.6/24. 5 32 1. 0 L-2 Pd2 (dba)3 0.1 2 CS2CO3 2 71.5/56. 7

Catalysis Examples 33 to 59: Suzuki reaction of aryl chlorides with phenylboronic acid/- pyrrolylphosphanes R-Ar-Cl + PhB (OH) 2-R-Ar-Ph Reagents: 3 mmol. of ArCl, 4.5 mmol. of PhB (OH) 2,6 mmol. of K3PO4, Pd (OAc) 2, Pd/L = 1 : 2,6 ml of toluene, 20 hours.

The reaction is carried out as a one-pot reaction under protecting gas. Working-up is carried out with 10 ml of each of methylene chloride and 1N sodium hydroxide solution. The reaction is monitored by means of GC, internal GC standard: hexadecane.

The starting materials used and the results of the conversions are summarised in Table 2.

Table 2 : Summary of the results of Catalysis Examples 33 to 59 No. R Ligand Conc. T [°C] C [%] Yield TON [mol. %] (averaged) f$l Aromatic compounds 33 4-CF3 PtBu 0.01 60 71-84 74 7400 34 4-COMe PtBu2 0.01 60 100 100 10, 000 35 4-CN PtBu2 0.01 60 100 100 10,000 36 H PtBu2 0.01 60 83-98 96 9600 37 4-Me PtBu2 0.01 60 98-100 99 9900 38 4-Ome PtBu2 0.01 60 73-89 80 8000 No. R Ligand Conc. T [°C] C [%] Yield TON [mol. %] (averaged) [%] 39 2-CF3 PtBu2 0.05 60 91 40 41 42 2-COMe PtBu2 0.05 60 78-84 85 43 2-COme PCy2 0.05 60 55 2-CF344 2-COm3 Pad2 0.05 60 70 45 2-CN PtBu2 0.05 60 100 100 2000 40 2-CF3 PCy2 0.05 60 99 95 41 2-CF3 PAd2 0.05 60 75 42 2-COMe PtBu2 0.05 60 78-84 85 43 2-COMe PCy2 0.05 60 55 44 2-COMe PAd2 0.05 60 70 45 2-CN PtBu2 0.05 60 100 100 2000 46 2-CN PCy2 0.05 60 100 100 2000 47 2-CN PAd2 0.05 60 100 99 1980 48 2-Me PtBu2 0.01 60 80-87 81 8100 49 2-Ome PtBu2 0.01 60 97-100 97 9700 50 2-F PtBu2 0.01 60 100 97 9700 51 2, 6-Me2 PtBu2 0.05 60 20-22 16 320 52 2,6-Me2 PCy2 0.05 60 76 72 1440 53 2, 6-Me2 PAd2 0.05 60 18 15 300 Heterocycles 3-chloro- 54 PtBu2 0.01 60 99-100 99 9900 pyridine 2-chloro- 55 PtBu2 0.05 60 100 87 1740 56 PtBu2 0.05 100 97-100 90 indole 2-chloro- 57 PtBu2 0.05 100 99 0a) 0 benzoxazole 58 3-chloro-PtBu2 0.05 100 11 5 100 thiophen 59 PtBu2 0.05 10 100 99 1980 furfural a) unknown (not visible in the GC) decomposition products.

Both starting material and product withstand the basic working-up undamaged. Decomposition (> 60 %) but scarcely any product (< 10 %) is observed even at a reaction temperature of 60°C.

Examples 60 to 64: Examples of ligand syntheses Example 60: Synthesis of N-phenyl-2- (di-l-adamantyl- phosphino) pyrrole

o N TIMEDA, + Cl-PAd. hexane 1. 6 ml of TMEDA (15 mmol. ) are added to a suspension of 1.43 g (10 mmol.) of N-phenylpyrrole in 30 ml of hexane.

6. 25 ml of 1.6 molar n-butyllithium solution (10 mmol. ) are added at room temperature. The mixture is then heated for 2.5 hours at reflux temperature (solution 1). In another flask, 3.36 g (10 mmol. ) of di-1-adamantylchlorophosphane are mixed with 40 ml of hexane and heated to 76°C (solution 2). The boiling solution 1 is then slowly transferred into solution 2, which is at 76°C, by means of a cannula. The mixture is then boiled for a further 2 hours at reflux, the solution is cooled, and 20 ml of water are added thereto. The organic phase is filtered off over magnesium sulfate. The solution is concentrated in vacuo; 15 ml of toluene are added thereto, and the mixture is heated to 60°C and then cooled. After one day at room temperature, the product is filtered off. Yield: 3.3 g (75 %).

31P NMR (161 MHz, CDCl3) : 8 =-4. 5.

1H NMR (400 MHz, CDCl3) : 6 = 1. 7 (bs, 16H), 1.7-2. 0 (m, 22H), 6.4 (dd, Jl = 8.6, 12.8, J2 = 3.5, 1H), 6.75 (dd, Jl = 3.5, J2 = 1, 1H), 6.9-7. 0 (m, 1H), 7.25-7. 3 (m, 2H), 7. 35-7. 45 (m, 3H).

3C NMR (100.6 MHz, CDC13) : 6 = 28. 6 (d, JPC = 11.5), 37, 37. 5 (d, JPC = 17. 2), 41.6 (d, Jpc = 11. 5), 108. 2,119. 5

(d, JPC = 4.7), 125.8, 126 (d, Jpc = 10. 8), 127.3, 128.2, 128.3 (d, Jpc = 3.8), 141.6 (d, JPC = 1.9).

MS: m/z (%) : 443 (68), 308 (13), 172 (14), 135 (100), 107 (7), 93 (19), 79 (17).

HRMS: C3oH38NP : calc. 443.2742 ; found 443.26775.

Example 61: Synthesis of 1-mesityl-2- (dicyclohexyl- phosphino) imidazole N y2 N TMEDA, + hexane 1. 6 ml of TMEDA (15 mmol. ) are added to a suspension of 1.86 g (10 mmol. ) of N-mesitylimidazole in 30 ml of hexane.

6.25 ml of 1.6 molar n-butyllithium solution (10 mmol. ) are added at room temperature. The mixture is then heated for 2.5 hours at reflux temperature (solution 1). In another flask, 2.2 ml (10 mmol. ) of dicyclohexylchlorophosphane are mixed with 20 ml of hexane and heated to 60°C (solution 2).

The boiling solution 1 is then slowly transferred into solution 2, which is at 60°C, by means of a cannula. The mixture is then boiled for a further 1 hour at reflux, the solution is cooled, and 20 ml of degassed water are added thereto. The organic phase is filtered off over magnesium sulfate. The solution is concentrated in vacuo; 30 ml of pentane are added thereto, and the mixture is boiled for 1 hour at reflux. The product precipitates in crystalline form at-30°C and is filtered off while cold. Yield: 2.48 g (65 %).

31P NMR (161 MHz, CDC13) : 18. 9.

1H NMR (400 MHz, CDC13) : 8 = 0.9-1. 2 (m, 11H), 1.5-1. 7 (m, 11H), 1.9 (s, 6H), 1.9-2. 0 (m, 2H), 2.2 (s, 3H), 6.8-6. 9 (m, 3H), 7.3 (s, 1H).

3C NMR (100. 6 MHz, Cd13) 18.5, 20.9, 26.9, 27.5, 27.7 (d, J = 9. 5), 30.4 (d, J = 14. 3), 30.9 (d, J = 10.5), 34.6 (d, J = 9. 5), 122.7, 129.2, 131.5, 134.9, 135.5, 138.2, 147.5 (d, J = 16.2).

MS: m/z (%) : 382 (11), 299 (100), 217 (24), 202 (7), 185 (27), 83 (7), 55 (21).

Example 62: Synthesis of N-(2-methoxyphenyl)-2-(dicyclo- hexylphosphino) pyrrole a) Synthesis of N- (2-methoxyphenyl) pyrrole NH2 r-\ OCH3 HOAc CH30 0 O /1 O oC h pale 2 -75 Lit.: Faigl, F.; Fogassy, K.; Thuner, A.; Toke, L.; Tetrahedron 1997,53, 4883.

10. 95 g (83 mmol.) of 1 and 4.7 g (38 mmol.) of 2 are refluxed for 2 hours in 10 ml of glacial acetic acid. The colour of the solution changes from yellow through red to black. The mixture is then diluted with 75 ml of distilled water and extracted twice with 100 ml of CHzCl2. Na2CO3 is added to the black organic solutions. After filtration and concentration (20 mbar, 50°C), a black oil is obtained and is distilled in vacuo. Yield: 4.45 g (25.7 mmol.; 75 %).

1H NMR (25°C, CDC13) : 8 (ppm) = 3. 8 (s, 3H), 6.3 (t, J = 2.2 Hz, 2H), 7.0 (m, 4H), 7.3 (m, 2H). b) Synthesis of N- (2-methoxyphenyl)-2- (dicyclohexyl- phosphino) pyrrole /\ N/CYZP N OCH3 hexane, 'k' beige solid (1)

3.14 ml (15 mmol. ) of N, N, N', N', N"-pentamethyldiethylene- triamine (PMDTA) are added to a solution of 1.73 g (10 mmol. ) of 1 in 30 ml of hexane. A solution (1.6 M in hexane) of n-BuLi (6.25 ml, 10 mmol. ) is added dropwise.

After 3 hours under reflux (75°C), the colour of the solution has changed from yellow to black. Without cooling this mixture, 2.2 ml (10 mmol. ) of chlorodicyclohexyl- phosphane dissolved in 20 ml of hexane are added dropwise.

Refluxing is carried out for a further one hour. The colour of the solution lightens to orange, and a white precipitate forms. After cooling to room temperature, 30 ml of water are added to the mixture. The orange organic phase is extracted 3 times using 20 ml of hexane each time. The combined organic phases are washed with 10 ml of water and filtered over Na2SO4. The solvent is removed in vacuo (45°C). The viscous orange residue is refluxed for 30 minutes in 30 ml of MeOH. On cooling to RT, the product precipitates and is filtered off (1.1 g, 30 %).

1H NMR (25°C, C6D6) : 8 (ppm) = 1. 1-1.9 (m, 22H), 3.2 (s, 3H), 7.0 (m, 4H), 6.5-7. 2 (m, 3H).

3C NMR (25°C, C6D6): 8 (ppm) = 27. 2,27. 7,27. 8,29. 6, 30.9, 34.9, 55.1, 109.8, 111.8, 116. 5,116. 6, 120.2, 123.6, 129.3, 130.9, 136.3, 156.0.

31P NMR (25°C, C6D6) : 8 (ppm) =-26. 8.

Example 63: Synthesis of N-phenyl-2- (dicyclohexyl- phosphino) indole a) Synthesis of N-phenylindole r /i Cut, N han + i N 110 H (1) W Lit.: Synthesis: Klapars, A.; Antilla, J.; Huang, X.; Buchwald, S. J. Am. Chem. Soc. 2001, 123, 7727. Analysis: (a) Nishio, T. J. Org. Chem. 1988,53, 1323. (b) Beller, M.; Breindl, C.; Riermeier, T.; Tillack, A. J. Org.

Chem. 2001, 66, 1403.

0.19 g (0.1 mmol. ) of CuI, 2.34 g (20 mmol. ) of 1,8. 82 g (42 mmol. ) of K3PO4, 0.48 ml (4 mmol. ) of 1, 2-diaminocyclo- hexane and 3.16 ml (30 mmol. ) of 2 are stirred for 24 hours at 110°C in 20 ml of dry dioxane. The mixture is then diluted with 50 ml of ethyl acetate. The violet precipitate is filtered off over silica gel, yielding a yellow solution, which is concentrated in vacuo (20 mbar, 50°C).

The orange oil that remains is purified by column chromatography (silica gel, hexane/ethyl acetate 98/2).

Yield: 3.0 g (15.5 mmol.; 75 %).

1H NMR (25°C, CDC13) : 8 (ppm) = 6. 45 (m, 1H), 6.9-7. 5 (m, 10H).

13C NMR (25°C, CDC13): 8 (ppm) = 104. 1,111. 1,120. 9,121. 7, 122.9, 124. 9, 126. 9,128. 5,129. 9,130. 1,130. 6,132. 1, 136.4, 140.3. b) Synthesis of N-phenyl-2- (dicyclohexylphosphino) indole r > N N T\EDA. BuLi + CIPCy_ hexane, white (1) 1.6 ml (15 mmol. ) of TMEDA are added to 1.93 g (10 mmol.) of 1 in 30 ml of hexane. A solution (1.6 M in hexane) of n- BuLi (6. 25 ml, 10 mmol. ) is added dropwise. After 3 hours' reflux (75°C), the colour has deepened from yellow to orange. without cooling, a solution of 2.2 ml (10 mmol. ) of chlorodicyclohexylphosphane in 20 ml of hexane is added dropwise. Refluxing is carried out for a further one hour, the colour of the mixture lightening again and a white solid precipitating. After cooling, 30 ml of water are added to the mixture. The aqueous phase is extracted 3 times using 20 ml of hexane each time. The combined organic phases are washed with 10 ml of water, dried over Na2SO4 and concentrated in vacuo (45°C). The yellow residue is boiled for 30 minutes in 30 ml of MeOH. After cooling to RT, the resulting product is filtered off (660 mg, 17 %).

31P NMR (25°C, C6D6): 8 (ppm) =-24-8- Example 64: Synthesis of N- (naphthyl)-2- (dicyclohexyl- phosphino) pyrrole a) Synthesis of N-naphthylpyrrole NH2 HOAX Ho CH30 OCHs// y (2) (1) (3) Icq 50%

¢3Lit. : Analysis: (a) Paredes, E.; Biolatto, B.; Kneeteman, M.; Mancini, P. Tetrahedron Lett. 2000, 41, 8079. (b) Gross, H. Chem. Ber. 1962, 95, 2270.

10. 95 g (83 mmol. ) of 1 are added to a violet solution of 5.44 g (38 mmol.) of 2 in 10 ml of glacial acetic acid. The resulting brown solution is refluxed for 3 hours under argon (120°C), whereupon its colour changes to black. The solution is concentrated to half the volume in vacuo (20 mbar, 50°C) before being hydrolysed with 20 ml of water. The organic phase is extracted with CH2C12 (3 x 30 ml), dried over Na2SO4 and concentrated (20 mbar, 50°C), there being obtained a black oil which is purified by column chromatography (silica gel, hexane/ethyl acetate 85/15). Yield: 3.53 g (18.3 mmol. ) of a red oil which crystallises at-25°C (pink crystals).

1H NMR (25°C, CDCl3) : 8 (ppm) = 6. 3 (t, J = 2.2 Hz, 2H), 6.7 (t, J = 2.2 Hz, 2H), 6.9-7. 2 (m, 4H), 7.3 (d, 8.1 Hz, 1H), 7.4 (d, 8.1 Hz, 1H), 7.7 (d, 8.1 Hz, 1H).

3C NMR (25°C, CDC13) : 6 (ppm) = 110. 0, 123.6, 123.8, 123.9, 125.7, 126.9, 127.4, 128.2, 130.7, 134.9, 139.0.

Elemental analysis : found (%) C 86.7 (th: 87.0), H 5.89 (5.70), N 7.29 (7.30). b) Synthesis of N- (naphthyl)-2- (dicyclohexylphosphino)- pyrrole 0 0 /\/\ N P CI-PCy, hexane, yellow (1)

1.6 ml (15 mmol. ) of TMEDA are added to a solution of 1.93 g (10 mmol. ) of 1 in 30 ml of hexane. A solution (1. 6 M in hexane) of n-BuLi (6.25 ml, 10 mmol. ) is added dropwise. After 3 hours'reflux (75*C), the colour has changed from orange through green to black. Without cooling, a solution of 2.2 ml (10 mmol. ) of chlorodicyclo- hexylphosphane in 20 ml of hexane is added dropwise and refluxing is carried out for a further one hour. The colour of the solution changes to yellow, and a white precipitate forms. After cooling to RT, 30 ml of water are added to the mixture. The aqueous phase is extracted 3 times using ml of hexane each time. The combined organic phases are washed with 10 ml of water, dried over Na2SO4 and concentrated in vacuo (45°C). The orange oil that remains is refluxed for 30 minutes in 30 ml of MeOH (60°C). On cooling to-25°C, the product precipitates in the form of a yellow solid and is filtered off (0.9 g, 24 %).

31P NMR (25°C, C6D6) : 8 (ppm) =-23. 3.

Example 65: ligands: /\/\/\ N 4 1 (15) 7 (15) 2R=Cy (80) 6R=Su (15) 3 R = Bu (75) 4 R = Ad (85) Narylpyrrole CON N PR2 PBU2 i i i 8 (60) 11 (50) 13 (10) 9 (50) 12 (90) 10 R = Ad (45) N-arylindole

General procedure: In a three nacked 100 ml round bottom flask with reflux condenser, N-arylpyrrole (or N-arylindole or N- arylimidazole) (10 mmol) was dissolved in 20 ml of freshly distilled n-hexane under argon. TMEDA (15 mmol) was added followed by n-BuLi (10 mmol, 1.6 M in hexane) at room temperature. The reaction mixture was refluxed for 3 h. A solution of the corresponding chlorophosphine (10 mmol in 5 ml hexane) was slowly added via syringe. The mixture was further refluxed for lh. After cooling to room temperature, degassed water (15 ml) was added and the mixture was stirred to get a clear solution. The aqueous layer was extracted with hexane (2x 15 ml) and the combined organic layers were washed with degassed water (15 ml). The solution was dried over Na2SO4 and concentrated at 45 °C to get a viscous liquid which was recrystallized from methanol or toluene.

Example 66: Catalytic amination of aryl chlorides A 30 mL pressure tube was loaded with Pd (OAc) 2 (0. 025 mmol), the ligand (0. 050 mmol), NaOtBu (6.0 mmol) and was purged by argon for 30 minutes. Then, were successively added under argon, toluene (5 mL), the aryl chloride (5 mmol) and the amine (6 mmol). The mixture was stirred under argon at 120 °C for 20 hours. After reaction, it was diluted with diethylether (15 mL) and washed with water (10 mL). After extraction, the organic phase was dried over MgSO4, concentrated under vacuum and the final product was isolated by column chromatography (silicagel, hexane/ethyl acetate 90/10). Alternatively, diethyleneglycol-di-n- butylether or hexadecane was added as internal standard, and quantitative analysis was done by gas chromatography.

Table 1: Amination of chloro-benzene with aniline using ligands 1 to 10: comparison of the activity. Entry Ligand Conv. [%] fa3 Yield [%] a T. O. N. I 2 i r _ 1 2 f i rN\ PiBu2. 3 136 fez NPAdz 4 76 152 f i 1J\ PtBu2 5 I r /\ 6 7 CH3'ß 4 Cl. CH3 O' 13 9 18 6 i Q PlBu2 cob. \ 10 N 46 92 6 i 5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 0.5 mol% Pd (OAc) 2,1 mol% ligand, 5 mL toluene, 48 h, 120 °C.

[a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether as internal standard.

Table 2 : Various aminations of chloro-benzene using ligand 9. Y chloride CI 94 w ce 2 CI f-- ci H C ci vN\JO ci CI H 94 l H 7 fT'Y1 fTY 100 95 100 i cl 1 zu 5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 0.5 mol% Pd (OAc) 2,1 mol% ligand, 5 mL toluene, 20 h, 120 °C. Reaction time has not been minimized. [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether or hexadecane as internal standard. [b] The reaction was conducted within 48 hours. [c] Ligand 5 was used (2 equiv/Pd).

Table 3: Various aminations of functionalized aryl-chlorides and chloro-pyridines using ligand 9. Entry Aryl-.-. chloride J 0 NHBu 1 ci T NHBU / ci 2 88 Cl NHBu H2N 100 95 CI cc 10 co"" ci 1 100 c. W , H'100 ce 7 100 91 XI ^ 8 HN CN CON NHBu CH /100 N 10 CH30aCi CH30 ci cl 11 /H Caf 3 ci cl 12 , , CF3 13 -Ql) F F F 14 99/Lig. H 15 b 100 . 16 -0 -N 99/lit. 17 ''HNO ''C)'100 99/Lig. 8 CH30 18 ci zu Ci 19 (b] 99 N N Conv. Yield5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 0.5 mol% Pd (OAc) 2,1 mol% ligand, 5 mL toluene, 20 h, 120 °C. Reaction time has not been minimized. [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether or hexadecane as internal standard. [b] 1 mol% Pd (OAc) 2,2 mol% ligand.

Table 4: Amination of 3-chloro-toluene with N-methyl- aniline: variations of temperature and catalyst loading <BR> <BR> <BR> <BR> Entry mol% Pd L/Pd T'Coav. Yield TON<BR> [°C] [%][a] [%][a] 1 0. 5 2 120 100 95 190 2 0. 5 2 100 100 92 184 3 0.5 2 80 100 90 180 4 0. 5 2 60 100 89 178 5 0.5 2 40 100 90 180 6 0.25 2 120 100 91 364 7 0.1 2 120 98 86 860 8 0.05 2 120 83 73 1460 9 0.025 2 120 70 62 2480 10 0.025 10 120 78 67 2680 11 0.01 2 120 24 23 2300 12 0. 01 25 120 39 33 3300 13 0.01 50 120 45 37 3700 5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 5 mL toluene, 20 h. Reaction time has not been minimized. [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether as internal standard.

Table 5: Various aminations of aryl-chlorides at low temperature using ligand 9. Aryl-Temp. CI 25 CH2 caf3 CRI 2 b) /H CF3 N 60 91 C30 c30 cri , 60 98 F 5 F ci 5 j H O 60 97 CI N ¢> 6 5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 0.5 mol% Pd (OAc) 2, 1 mol% ligand, 5 mL toluene, 20 h. Reaction time has not been minimized. [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether or hexadecane as internal standard. [b] 1 mol% Pd (OAc) 2,2 mol% ligand.