ZHAN JAMES ZHENG-YUN (CN)
| WO2007003135A1 | 2007-01-11 | |||
| WO2005053843A1 | 2005-06-16 | |||
| WO2004035596A1 | 2004-04-29 |
| CN101684075A | 2010-03-31 |
| What is claimed is: 1. A ligand of metal complex having the following structure la or lb la lb Wherein: Z is CH2= or Ts HN= m = 0 or 1, n = 0 or 1; When m = 0, Y is CH2, H, oxygen, nitrogen, carbonyl, imino, Ci-C2o alkoxy, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, NH, Ci-C20 alkyl, Ci-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C2o heteroaryl, Ci-C2o alkylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o arylcarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; "Y— X" is either single bond or double bond; When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C20 alkyl, C6-C20 aryl, C6-C20 aryloxy, C2-C20 heterocyclic aryl, Ci-C20 alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; R1 is H, Ci-C20 alkyl, C2-C20 alkenyl, C6-C20 aryl, C6-C20 arylenyl, Ci-C20 alkoxy, Ci-C2o alkylthio, C6-C2o arylthio, C6-C2o aryloxy, C3-C2o heteroaryl or C2-C2o heterocyclic group; R2 is H, Ci-C2o alkyl, C6-C2o aryl, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkyoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o aminocarbonyl, C3-C2o heteroaryl or C2-C2o heterocyclic group; E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, Ci-C2o alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C2o alkenyloxy, Ci-C2o silanyl, Ci-C2o alkylsilyloxy, C6-C2o aryl, C6-C2o aryloxy, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, amino, Ci-C2o alkylaminocarbonyl, C6-C2o arylaminocarbonyl, Ci-C2o alkylamido, C6-C2o arylamido, Ci-C2o alkylaminosulfonyl, C6-C2o arylamino sulfonyl, Ci-C2o sulfonylamido, C3-C2o heteroaryl or C2-C2o heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group. 2. The ligand of metal complex according to claim 1, wherein the structure Ia-Ib, Z is CH2= or TsNHN=; m = 0 or 1, n = 0 or 1 ; When m = 0, Y is CH2, H, oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C6-Ci5 aryloxy, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, NH, C1-C15 alkyl, C1-C15 alkoxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C3-Cis heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 arylcarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; "Y— X" is either single bond or double bond. When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, C1-C15 alkyl, C6-Ci5 aryl, C6-Ci5 aryloxy, C2-Cis heterocyclic aryl, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; R1 is H, C1-C15 alkyl, C2-Ci5 alkenyl, C6-C15 aryl, C6-C15 arylenyl, C1-C15 alkoxy, C1-C15 alkylthio, C6-C15 arylthio, C6-C15 aryloxy, C3-Ci5 heteroaryl or C2-Ci5 heterocyclic group; R2 is H, C1-C15 alkyl, C6-C15 aryl, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C15 aminocarbonyl, C3-Ci5 heteroaryl or C2-Ci5 heterocyclic group; E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-Ci5 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-C15 aryl, C6-C15 aryloxy, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-C15 arylaminocarbonyl, C1-C15 alkylamido, C6-C15 arylamido, C1-C15 alkylaminosulfonyl, C6-C15 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-Ci5 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group. 3. The ligand of metal complex according to claim 2, wherein the structure Ia-Ib, Z is CH2= or Ts HN=; m = 0 or 1, n = 0 or 1 ; When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C8 alkoxy, C6-C8 aryloxy, Ci-C8 alkoxycarbonyl, C6-C8 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-Ci2 heterocyclic amino group; When m = 1, X is nitrogen, oxygen, sulfur, CH, CH2, carbonyl; Y is oxygen, nitrogen, CH, CH2, imino, H, C1-C15 alkyl, Ci-C8 alkoxy, C6-Ci5 aryl, C6-Ci2 aryloxy, C3-Ci2 heteroaryl, Ci-C8 alkylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 arylcarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group; "Y— X" is either single bond or double bond. When n = 1, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C8 alkyl, C6-C8 aryl, C6-C8 aryloxy, C2-C8 heterocyclic aryl, Ci-C8 alkylamino, C6-C8 arylamino or C2-C8 heterocyclic amino group; R1 is H, Ci-C8 alkyl, C2-C8 alkenyl, C6-C12 aryl or C6-C12 arylenyl; R2 is methyl, ethyl, isopropyl, Ci-C8 alkyl or C6-Ci2 aryl; 1 2 3 4 5 6 7 E, E , E , EJ, E , E E° and E' are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl, Ci-C8 sulfonylamido, C3-C12 heteroaryl or C2-C8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group. 4. The ligand of metal complex according to claim 3, wherein the structure Ia-Ib, Z is CH2= or TsNHN=; m = 0 or 1, n = 0 or 1; When m = 0, Y is CH2, H, C1-C4 alkoxy, C1-C4 alkylamino or C6-C9 arylamino group; When m = 1, X is nitrogen, C1-C3 alkylamino, CH, CH2, or carbonyl; Y is oxygen, nitrogen, imino, NH, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, or C6-C9 arylamino; "Y— X" is either single bond or double bond; When n = 1, X1 is CH2, substituted or unsubstituted phenyl, or carbonyl; Y1 is oxygen or carbonyl; R1 is H; when n = 1, R2 is methyl, ethyl, or isopropyl; when n = 0, R2 is H, halogen, C1-C4 alkyl or C1-C4 alkoxy in structure la. E is H, halogen, nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl; E1 and E2 are each H, halogen, C1-C4 alkyl or C1-C4 alkoxy; E3 is H; E4 is H or C1-C4 alkyl; E5 and E6 is H, halogen, C1-C4 alkyl or Ci-C6 alkoxy; E7 is H or C1-C4 alkyl. 5. A transition metal com lex having the following structure Ila or lib, Ila lib wherein: m = 0 or 1, n = 0 or 1; When n = 0; p = 0 or 1; when n = 1, p = 0; M is a transition metal; L1 and L2 are the same or different and each selected from halogen anion (CI", Br" or I"), RC(0)0" or ArO" anion; L is an electron-donating ligand; When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, Ci-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C20 heteroaryl, Ci-C2o alkylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o arylcarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; "Y— x" is either single bond or double bond; When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C2o alkoxy, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o alkylimino, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; When n = 0 and p = 1, L3 is an electron-donating ligand; When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C2o alkyl, C6-C2o aryl, C6-C2o aryloxy, C2-C2o heterocyclic aryl, Ci-C2o alkylamino, C6-C2o arylamino or C2-C2o heterocyclic amino group; R1 is H, Ci-C20 alkyl, C2-C20 alkenyl, C6-C20 aryl, C6-C20 arylenyl, Ci-C20 alkoxy, Ci-C2o alkylthio, C6-C2o arylthio, C6-C2o aryloxy, C3-C2o heteroaryl or C2-C2o heterocyclic group; R2 is H, Ci-C2o alkyl, C6-C2o aryl, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkyoxycarbonyl, C6-C2o aryloxycarbonyl, Ci-C2o aminocarbonyl, C3-C2o heteroaryl or C2-C2o heterocyclic group; E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, Ci-C2o alkyl, Ci-C2o alkoxy, Ci-C2o alkylthio, C2-C2o alkenyloxy, Ci-C2o silanyl, Ci-C2o alkylsilyloxy, C6-C2o aryl, C6-C2o aryloxy, Ci-C2o alkylcarbonyl, C6-C2o arylcarbonyl, Ci-C2o alkoxycarbonyl, C6-C2o aryloxycarbonyl, amino, Ci-C2o alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylaminosulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, arylox halogen atom or heterocyclic group. 6. The transition metal complex according to claim 5, wherein L is heterocyclic carbene ligand or phosphine P(R8)2( 9) having the following structure Ilia, Illb, IIlc, or Hid: Ilia Illb IIlc Hid Wherein, q = 1, 2 or 3; R4 and R5 are each C1-C20 alkyl, C6-C20 aryl, C1-C20 alkylamido, C6-C20 arylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group; R6 and R7 are each H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyloxy, C1-C20 silanyl, C1-C20 alkylsilyloxy, C2-C20 heterocyclic, C6-C20 aryl, C6-C20 aryloxy, C1-C20 alkylcarbonyl, C6-C20 arylcarbonyl, C1-C20 alkoxycarbonyl, C6-C20 aryloxycarbonyl, amino, C1-C20 alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylaminosulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group; R8 and R9 are each C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C20 heteroaryl or C2-C20 heterocyclic group. 7. The transition metal complex according to claim 6, wherein L is formula Ilia or Hid; and in Ilia, q = 1 or 2, R4 and R5 each is aryl, R6 and R7 each is H. 8. The transition metal complex according to claim 6, wherein L is Ilia or Hid; and in Ilia, q = 1, R4 and R5 each is 2,4,6-trimethylphenyl, R6 and R7 each is H; or in Hid, R8 and R9 each is cyclohexyl (Cy). 9. The transition metal complex according to claim 5, wherein the structure Ila or lib: M is ruthenium ( u), wolfram (W) or nickel (Ni); m = 0 or 1, n = 0 or 1; L1 and L2 each is chloride (Cf); L is Ilia or Hid; wherein q, R4, R5, R6, R7, R8 and R9 each is as defined in claim 6; R1, R2, E, E1, E2, E3, E4, E5, E6 and E7 each is as defined in claim 2. When m = 0, Y is oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C6-Ci5 aryloxy, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-C15 heterocyclic amino group; When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, C1-C15 alkoxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C3-C15 heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 arylcarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; "Y— X" is either single bond or double bond. When n = 0, p = 0 or 1; when n = 1, p = 0. When n = 0 and p = 1 , L3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-Cis alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C1-C15 alkylcarbonyl, C6-Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylamino sulfonyl, C6-Ci5 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-Cis heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group. When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, C1-C15 alkyl, C6-Ci5 aryl, C6-Ci5 aryloxy, C2-Cis heterocyclic aryl, C1-C15 alkylamino, C6-Ci5 arylamino or C2-Cis heterocyclic amino group; 10. The transition metal complex according to claim 9, wherein the structure Ila or lib, When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C8 alkoxy, C6-Ci2 aryloxy, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group; When m = 1, X is oxygen, nitrogen, sulfur, CH, CH2, carbonyl; Y is nitrogen, oxygen, CH, CH2, imino, Ci-C8 alkoxy, C6-Ci2 aryl, C6-Ci2 aryloxy, C3-Ci2 heteroaryl, Ci-C8 alkylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 arylcarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylimino, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group; "Y— X" is either single bond or double bond. When n = 0, p = 0 or 1 ; when n = 1, p = 0. When n = 0 and p = 1 , L3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-Ci2 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylamino sulfonyl, Ci-C8 sulfonylamido, C3-Ci2 heteroaryl or C2-C8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group; When n = 1 and p = 0, X1 and Y1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH2, Ci-C8 alkyl, C6-Ci2 aryl, C6-Ci2 aryloxy, C2-Ci2 heterocyclic aryl, Ci-C8 alkylamino, C6-Ci2 arylamino or C2-C8 heterocyclic amino group; R1 is H, Ci-C8 alkyl, C2-C8 alkenyl, C6-C12 aryl or C6-C12 arylenyl; R2 is methyl, ethyl, isopropyl, Ci-C8 alkyl or C6-Ci2 aryl; E, E1, E2, E3, E4, E5, E6 and E7 are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, C2-C8 alkenyloxy, Ci-C8 silanyl, Ci-C8 alkylsilyloxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C8 alkylcarbonyl, C6-Ci2 arylcarbonyl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl, Ci-C8 sulfonylamido, C3-C12 heteroaryl or C2-C8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group. 11. The transition metal complex according to claim 10, wherein the structure Ila or lib: M is ruthenium; L is Ilia or Hid; and in Ilia, q = 1, R4 and R5 each is 2,4,6-trimethylphenyl, R6 and R7 each is H; or in Hid, R8 and R9 each is cyclohexyl (Cy). L1 and L2 each is chloride anion; m = 0 or 1, and n = 0 or 1; When m = 0, Y is CH2, H, C1-C4 alkoxy, C1-C4 alkylamino or C6-C9 arylamino group; When m = 1, X is nitrogen, C1-C3 alkylamino, CH, CH2, or carbonyl; Y is oxygen, nitrogen, imino, NH, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, or C6-C9 arylamino; "Y— X" is either single bond or double bond; When n = 0, p = 0 or 1; when n = 1, p = 0; When n = 0 and p = 1 , L3 is one substituted pyridine at the meta-position or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to ruthenium cation, wherein the substituents at the meta-position or para-position of pyridine are each selected from halogen, nitro, C1-C3 alkyl, C1-C3 alkoxy, Ci-C6 alkylamino, unsubstituted or substituted C6-Ci2 aryl; When n = 1, X1 is CH2, substituted or unsubstituted phenyl, or carbonyl; Y1 is oxygen or carbonyl; R1 is H; when n = 1, R2 is methyl, ethyl, or isopropyl; when n = 0, R2 is H, halogen, C1-C4 alkyl or C1-C4 alkoxy in structure Ila. E is H, halogen, nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, Ci-C8 alkylaminosulfonyl, C6-Ci2 arylaminosulfonyl; E1 and E2 are each H, halogen, C1-C4 alkyl or C1-C4 alkoxy; E3 is H; E4 is H or C1-C4 alkyl; E5 and E6 is H, halogen, C1-C4 alkyl or C1-C5 alkoxy; E7 is H or C1-C4 alkyl. 12. A method of carrying out a metathesis reaction with olefin substrate, comprising intramolecular ring-closing metathesis (RCM), intermolecular cross metathesis (CM) or ring-opening metathesis polymerization (ROMP) of cyclo-olefin substrate in the presence of the catalyst of claim 5. 13. The method according to claim 12, wherein cyclo-olefin substrate for ROMP is selected from dicyclopentadiene (DCPD), norbornene, cyclooctene, or a kind of tensional cycloolefin; each is optionally substituted or unsubstituted with one or more of F, CI, Br, C1-C15 alkyl, Ci-C 15 alkoxy, C1-C15 alkylthio, C2-Ci5 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C1-C15 alkylcarbonyl, C6-Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylaminosulfonyl, C6-Ci5 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C2-Cis heterocyclic group. 14. A cycloolefin substrate having the following structure Via- Vic; Via VIb Vic Wherein, r = 1, 2, 3 or 4; s = 1, 2, 3 or 4; A is O, S, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 aryloxy, C1-C15 alkylthio, C1-C15 alkoxycarbonyl, C1-C15 alkylamino, C6-Ci5 arylamino, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, or C1-C15 heterocyclic amido group; G is a group of compounds with specific properties and uses; each is optionally selected from commercial drugs or liquid crystal monomers; R10 and R11 are each H, halogen, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C2-C15 heterocyclic, C3-C15 heterocyclic aryl, C1-C15 alkylcarbonyl, C1-C15 alkyloxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C1-C15 alkylsulfonyl, C1-C15 alkylsulfonamido, liquid crystal monomer or modified pro-drug; "Linker" is C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, Ci-C 15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylsulfonamido, C6-Ci5 arylsulfonamido, C3-C15 heteroaryl or C2-C15 heterocyclic group. 15. The cycloolefin substrate according to claim 14, wherein r =1, 2, 3 or 4; s = 1, 2, 3 or 4;: A is O, S, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 aryloxy, C1-C15 alkylthio, Ci-C8 alkoxycarbonyl, Ci-C8 alkylamino, C6-Ci2 arylamino, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, or Ci-C8 heterocyclic amido group; G is a kind of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomers or modified prodrugs; R10 and R11 are each H, halogen, Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, Ci-C8 alkylsilyoxy, C6-Ci2 aryloxy, C6-Ci2 aryl, C2-Q heterocyclic, C3-C12 heterocyclic aryl, Ci-C8 alkylcarbonyl, Ci-C8 alkyloxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, Ci-C8 alkylsulfonyl, Ci-C8 alkylsulfonamido, liquid crystal monomer or modified pro-drug; "Linker" is Ci-C8 alkyl, Ci-C8 alkoxy, Ci-C8 alkylthio, Ci-C8 alkylsilyoxy, C6-Ci2 aryloxy, C6-Ci2 aryl, Ci-C8 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, Ci-C8 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, Ci-C8 alkylamido, C6-Ci2 arylamido, Ci-Cg alkylsulfonamido, C6-Ci2 arylsulfonamido, C3-C12 heteroaryl or C2-C8 heterocyclic group. 16. The cycloolefin substrate according to claim 15, wherein in structure Via- Vic, r = 1 or 2, and s = 1 or 2; A is O, CH2, C1-C5 alkyl-amino, C1-C5 alkoxy, C1-C5 alkylaminocarbonyl or C1-C5 heterocyclic amido group; "Linker" is Ci-C6 alkyl, C1-C5 alkoxy, C1-C5 alkylthio, C1-C5 alkoxycarbonyl, C1-C5 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, C1-C5 alkylamido or C6-Ci2 arylamido group; R10 and R11 are each H, C1-C5 alkoxy, C6-Ci2 aryloxy, C1-C5 alkoxycarbonyl, C6-Ci2 aryloxycarbonyl, C1-C5 alkylaminocarbonyl, C6-Ci2 arylaminocarbonyl, C1-C5 alkylamido, C6-Ci2 arylamido, liquid crystal monomer or modified prodrugs. 17. The cycloolefin substrate according to claim 15, wherein G is a kind of optionally modified prodrug of commercial drug Lipitor having the following structure Vlla-VIId: Vila Vllb VIIc Vlld Wherein R12 is cyclopropyl, C1-C15 alkly, C3-C15 cycloalkyl, C1-C15 alkoxy, C6-Ci5 aryl, C6-Ci5 aryloxy, C1-C15 alkylamino, C6-Ci5 arylamino, C1-C15 alkylsulfonamido, C6-Ci5 arylsulfonamido, C3-C15 heterocyclic aryl or C2-C15 heterocyclic group. 18. The cycloolefin substrate according to claim 17, wherein R12 is cyclopropyl, Ci-C6 alkly, C3-C6 cycloalkyl, Ci-C6 alkoxy, C6-Ci2 aryl, C6-Ci2 aryloxy, Ci-C6 alkylamino, C6-Ci2 arylamino, Ci-C6 alkylsulfonamido, C6-Ci2 arylsulfonamido, C3-C12 heterocyclic aryl or C2-C6 heterocyclic group. 19. A method of making a quality-modified polymer having the following structure Villa or Vlllb in the presence of one or two more mixed catalysts selected from claim 5. Villa Vlllb (PDCPD) 20. A functional polymer, comprising a modified prodrug or functional G having the following structure IXa-IXc: IXa IXb Wherein: r = 1, 2, 3 or 4; s = 1, 2, 3 or 4; A is O, S, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 aryloxy, C1-C15 alkylthio, C1-C15 alkoxycarbonyl, C1-C15 alkylamino, C6-Ci5 arylamino, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, or C1-C15 heterocyclic amido group; G is a group of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomer or modified prodrugs; R10 and R11 are each H, halogen, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C2-C15 heterocyclic, C3-C15 heterocyclic aryl, C1-C15 alkylcarbonyl, C1-C15 alkyloxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C1-C15 alkylsulfonyl, C1-C15 alkylsulfonamido, liquid crystal monomer or modified pro-drug; "Linker" is C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C6-Ci5 aryloxy, C6-Ci5 aryl, C1-C15 alkoxycarbonyl, C6-Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-Ci5 arylaminocarbonyl, C1-C15 alkylamido, C6-Ci5 arylamido, C1-C15 alkylsulfonamido, C6-Ci5 arylsulfonamido, C3-C15 heteroaryl or C2-C15 heterocyclic group. 21. The functional polymer according to claim 20, wherein r, s, A, "Linker", R10 and R11 each is as defined in claim 16; Wherein G is a kind of optionally modified pro-drug of Lipitor having the following structure VHa-VIId: Vila Vllb VIIc Vlld Wherein: R12 is as defined in claim 18. 22. A process of making a quality-modified polymer Villa- VHIb or functional polymer IXa-IXb in the presence of one or two more mixed catalysts of claim 5. 23. A method of making functional polymers, comprising reacting one or more monomers in the presence of one or two more mixed catalysts of claim 5. |
The present invention relates to novel carbene ligands and their incorporated ruthenium catalysts, which are highly active and selective for different kinds of olefin metathesis reactions. The invention also relates to preparation of new ruthenium complexes and the use thereof in metathesis, especially effective for preparation of various functional polymers by ROMP reacton.
BACKGROUND OF THE INVENTION
Since Richard R. Schrock and Robert H. Grubbs prepared two kinds of metathesis catalysts with transition metal carbene structure in the 1990's, it has been drawning extensive attention in the development of more active and selective ruthenium catalysts for different kinds of olefin metathesis reactions, e.g., ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM), and cross metathesis (CM).
So far, some useful ruthenium complexes have been reported as active metathesis catalysts (la-lb and 2a-2f in Scheme 1) for RCM and ROMP reactions (Grubbs et al, J. Am. Chem. Soc. 1992, 114, 3974-3975, Org. Lett. 1999, 1, 953-956, WO2007081987A1 ; Hoveyda et al, J. Am. Chem. Soc. 1999, 121, 791-799, J. Am. Chem. Soc. 2000, 122, 8168-8179; Yamaguchi et al, Chem. Commun. 1998, 1399-1400; Zhan et al, US20070043180A1, WO 2007003135A1; Grela et al, WO2004035596A1 ; Slugovc et al, Organometallics 2004, 23(15), 3623-3626 for catalyst 2d; and Organometallics 2005, 24(10), 2255-2258 for catalyst 2e). However, a disadvantage of all reported ruthenium catalysts is obviously substrate-dependent for different kinds of ruthenium catalysts in metathesis reactions, and it is still very difficult to find some active metathesis catalysts selective for RCM and ROMP reactions, respectively. Moreover, only a few metathesis catalysts could be used effectively to make high-strength and high-stiffness polydicyclopentadiene (PDCPD) material by ROMP reaction
la lb 2a 2b
Grubbs Catalyst (1st) Grubbs Catalyst (2nd) Hoveyda Catalyst Zhan Catalyst
2c 2d 2e 2f (Grela Catalyst)
Scheme 1 Structure of Some Active Catalysts for ROMP and RCM Reaction Currently ROMP reaction is broadly used for preparation of various high-strength and other functional polymers. To overcome the activity and selectivity problems for ROMP catalysts, it has become a goal to develop more active and selective metathesis catalysts as an alternative for ROMP and RCM reactions, especially in ROMP for effective preparation and modification of different functional polymer materials. It is significantly important to develop more active and selective ruthenium catalyst for ROMP reactions with different kinds of olefin substrates to prepare highly functional polymer materials and also to improve polymer properties.
SUMMARY OF THE INVENTION
The present invention relates to two classes of novel carbene ligands and their incorporated ruthenium complexes that can be used as highly active metathesis catalysts selective for RCM, CM, and ROMP reactions, respectively. The novel metathesis catalysts are ruthenium complexes with different kinds of new functionally substituted carbene ligands. The new ruthenium complexes of the invention can catalyze different kinds of metathesis reactions in a very effective manner and offer great advantage in activity and selectivity for different kinds of metathesis reactions, especially in ROMP effective for preparation of some functional polymer materials with unique chemical and physical properties. The novel ruthenium complexes of the invention have broad uses in the polymeric and pharmaceutical industries.
In the first aspect, the present invention provides a kind of compounds to form carbene ligands having the following structure la or lb:
la lb
Wherein Z is CH 2 = or Ts HN=;
m = 0 or 1, n = 0 or 1;
When m = 0, Y is CH 2 , H, oxygen, nitrogen, carbonyl, imino, Ci-C 2 o alkoxy, C 6 -C 2 o aryloxy, C 2 -C 2 o heterocyclic aryl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o alkylimino, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl; Y is nitrogen, oxygen, CH, CH 2 , imino, NH, Ci-C 20 alkyl, Ci-C 20 alkoxy, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 3 -C 2 o heteroaryl, Ci-C 2 o alkylcarbonyl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o arylcarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o alkylimino, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group; "Y— X" is either single bond or double bond;
When n = 1, X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , Ci-C 20 alkyl, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 2 -C 20 heterocyclic aryl, Ci-C 20 alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group;
R 1 is H, Ci-C 20 alkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, C 6 -C 20 arylenyl, Ci-C 20 alkoxy, Ci-C 2 o alkylthio, C 6 -C 2 o arylthio, C 6 -C 2 o aryloxy, C 3 -C 2 o heteroaryl or C 2 -C 2 o heterocyclic group;
R 2 is H, Ci-C 2 o alkyl, C 6 -C 2 o aryl, Ci-C 2 o alkylcarbonyl, C 6 -C 2 o arylcarbonyl, Ci-C 2 o alkyoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o aminocarbonyl, C 3 -C 2 o heteroaryl or C 2 -C 2 o heterocyclic group;
E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyloxy, C1-C20 silanyl, C1-C20 alkylsilyloxy, C6-C20 aryl, C6-C20 aryloxy, C1-C20 alkylcarbonyl, C6-C20 arylcarbonyl, C1-C20 alkoxycarbonyl, C6-C20 aryloxycarbonyl, amino, C1-C20 alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylamino sulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group;
In one preferred embodiment in the present invention, the formula Ia-Ib,
Z is CH 2 or Ts HN=;
m = 0 or 1, n = 0 or 1;
When m = 0, Y is CH 2 , H, oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C 6 -Ci5 aryloxy, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C 6 -Ci5 arylamino or C2-C15 heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl; Y is nitrogen, oxygen, CH, CH 2 , imino, NH, C1-C15 alkyl, C1-C15 alkoxy, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C3-C15 heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C 6 -Ci5 arylcarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C 6 -Ci5 arylamino or C2-C15 heterocyclic amino group; "Y— X" is either single bond or double bond.
When n = 1, X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , C1-C15 alkyl, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C2-C15 heterocyclic aryl, C1-C15 alkylamino, C 6 -Ci5 arylamino or C2-C15 heterocyclic amino group;
R 1 is H, C1-C15 alkyl, C2-C15 alkenyl, C6-C15 aryl, C6-C15 arylenyl, C1-C15 alkoxy, C1-C15 alkylthio, C6-C15 arylthio, C6-C15 aryloxy, C3-C15 heteroaryl or C2-C15 heterocyclic group;
R 2 is H, C1-C15 alkyl, C6-C15 aryl, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkyoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C 15 aminocarbonyl, C3-C15 heteroaryl or C2-C15 heterocyclic group;
E, E 1 , E 2 , E 3 J , E 4 , E 5 E 6° and E 7' are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C 2 -Ci 5 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C6-C15 aryl, C6-C15 aryloxy, C1-C15 alkylcarbonyl, C6-C15 arylcarbonyl, C1-C15 alkoxycarbonyl, C6-C15 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C6-C15 arylaminocarbonyl, C1-C15 alkylamido, C6-C15 arylamido, C1-C15 alkylamino sulfonyl, C6-C15 arylamino sulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C 2 -Ci 5 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
In one more preferred embodiment in the present invention, in the formula Ia-Ib, Z is CH 2 = or Ts HN=;
m = 0 or 1, n = 0 or 1 ;
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C 8 alkoxy, C 6 -C 8 aryloxy, Ci-C 8 alkoxycarbonyl, C 6 -C 8 aryloxycarbonyl, Ci-C 8 alkylimino, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -Ci 2 heterocyclic amino group;
When m = 1, X is nitrogen, oxygen, sulfur, CH, CH 2 , carbonyl; Y is oxygen, nitrogen, CH, CH 2 , imino, H, C1-C15 alkyl, Ci-C 8 alkoxy, C 6 -Ci5 aryl, C 6 -Ci 2 aryloxy, C 3 -Ci 2 heteroaryl, Ci-C 8 alkylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 arylcarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylimino, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -C 8 heterocyclic amino group; "Y— X" is either single bond or double bond.
When n = 1, X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , Ci-C 8 alkyl, C 6 -C 8 aryl, C 6 -C 8 aryloxy, C 2 -C 8 heterocyclic aryl, Ci-C 8 alkylamino, C 6 -C 8 arylamino or C 2 -C 8 heterocyclic amino group;
R 1 is H, Ci-C 8 alkyl, C 2 -C 8 alkenyl, C6-C 12 aryl or C6-C 12 arylenyl;
R 2 is methyl, ethyl, isopropyl, Ci-C 8 alkyl or C 6 -Ci 2 aryl;
E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, C 2 -C 8 alkenyloxy, Ci-C 8 silanyl, Ci-C 8 alkylsilyloxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, Ci-C 8 alkylcarbonyl, C 6 -Ci 2 arylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, Ci-C 8 alkylaminosulfonyl, C 6 -Ci 2 arylaminosulfonyl, Ci-C 8 sulfonylamido, C 3 -C 12 heteroaryl or C 2 -C 8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
In one most preferred embodiment in the present invention, the formula Ia-Ib Z is CH 2 = or Ts HN=;
m = 0 or 1, n = 0 or 1;
When m = 0, Y is CH 2 , NH, C 1 -C 4 alkoxy, C 1 -C 4 alkylamino or C 6 -C 9 arylamino group;
When m = 1, X is nitrogen, C 1 -C 3 alkylamino, CH, CH 2 , or carbonyl; Y is oxygen, nitrogen, imino, NH, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylamino, or C 6 -C 9 arylamino; "Y— X" is either single bond or double bond;
When n = 1, X 1 is CH 2 , substituted or unsubstituted phenyl, or carbonyl; Y 1 is oxygen or carbonyl;
R 1 is H;
when n = 1, R 2 is methyl, ethyl, or isopropyl; and when n = 0, R 2 is H, halogen, C1-C4 alkyl or C1-C4 alkoxy in structure la.
E is H, halogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, Ci-C 8 alkylaminosulfonyl, C 6 -Ci 2 arylaminosulfonyl;
E 1 and E 2 are each H, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
E 3 is H;
E 4 is H or C 1 -C 4 alkyl;
E 5 and E 6 is H, halogen, C 1 -C 4 alkyl or Ci-C 6 alkoxy;
E 7 is H or C 1 -C 4 alkyl.
In the second aspect, the present invention provides a kind of transition metal complex having the following structure Ila or lib:
Ila lib
Wherein: m = 0 or 1, and n = 0 or 1 ;
When n = 0; p = 0 or 1 ; when n = 1, p = 0;
M is a transition metal;
L 1 and L 2 are the same or different and each selected from halogen anion (CI " ,
Br " or I " ), RC(0)0 " or ArO " anion;
L is an electron-donating ligand;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl; Y is nitrogen, oxygen, CH, CH 2 , imino, Ci-C 20 alkoxy, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 3 -C 20 heteroaryl, Ci-C 2 o alkylcarbonyl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o arylcarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o alkylimino, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group; "Y— x" is either single bond or double bond;
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C 2 o alkoxy, C 6 -C 2 o aryloxy, C 2 -C 2 o heterocyclic aryl, Ci-C 2 o alkoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o alkylimino, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group;
When n = 0 and p = 1, L 3 is an electron-donating ligand;
When n = 1 and p = 0, X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , Ci-C 2 o alkyl, C 6 -C 2 o aryl, C 6 -C 2 o aryloxy, C 2 -C 2 o heterocyclic aryl, Ci-C 2 o alkylamino, C 6 -C 2 o arylamino or C 2 -C 2 o heterocyclic amino group;
R 1 is H, Ci-C 20 alkyl, C 2 -C 20 alkenyl, C 6 -C 20 aryl, C 6 -C 20 arylenyl, Ci-C 20 alkoxy, Ci-C 2 o alkylthio, C 6 -C 2 o arylthio, C 6 -C 2 o aryloxy, C 3 -C 2 o heteroaryl or C 2 -C 2 o heterocyclic group;
R 2 is H, Ci-C 2 o alkyl, C 6 -C 2 o aryl, Ci-C 2 o alkylcarbonyl, C 6 -C 2 o arylcarbonyl, Ci-C 2 o alkyoxycarbonyl, C 6 -C 2 o aryloxycarbonyl, Ci-C 2 o aminocarbonyl, C 3 -C 2 o heteroaryl or C 2 -C 2 o heterocyclic group; E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are each independently selected from the group consisting of H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyloxy, C1-C20 silanyl, C1-C20 alkylsilyloxy, C6-C20 aryl, C6-C20 aryloxy, C1-C20 alkylcarbonyl, C6-C20 arylcarbonyl, C1-C20 alkoxycarbonyl, C6-C20 aryloxycarbonyl, amino, C1-C20 alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylamino sulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group.
In preferred embodiment Ila or lib, L is heterocyclic carbene ligand or phosphine P(R 8 )2( 9 ) having the following structure Ilia, Illb, IIIc, or Hid:
Ilia Illb IIIc Hid
Wherein, q = 1, 2 or 3;
R 4 and R 5 are each C1-C20 alkyl, C6-C20 aryl, C1-C20 alkylamido, C6-C20 arylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group;
R 6 and R 7 are each H, halogen atom, nitro, amino, cyano, formyl, sulfinyl, sulfonyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C2-C20 alkenyloxy, C1-C20 silanyl, C1-C20 alkylsilyloxy, C2-C20 heterocyclic, C6-C20 aryl, C6-C20 aryloxy, C1-C20 alkylcarbonyl, C6-C20 arylcarbonyl, C1-C20 alkoxycarbonyl, C6-C20 aryloxycarbonyl, amino, C1-C20 alkylaminocarbonyl, C6-C20 arylaminocarbonyl, C1-C20 alkylamido, C6-C20 arylamido, C1-C20 alkylaminosulfonyl, C6-C20 arylamino sulfonyl, C1-C20 sulfonylamido, C3-C20 heteroaryl or C2-C20 heterocyclic group;
R 8 and R 9 are each C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aryl, C6-C20 aryloxy, C3-C20 heteroaryl or C2-C20 heterocyclic group.
In one preferred embodiment, wherein L is formula Ilia or Hid; and in Ilia, q =
1 or 2, R 4 and R 5 each is aryl, R 6 and R 7 each is H. In one more preferred embodiment, wherein L is Ilia or Hid; and in Ilia, q = 1, R 4 and R 5 each is 2,4,6-trimethylphenyl, R 6 and R 7 each is H; or in Hid, R 8 and R 9 each is cyclohexyl (Cy).
In another preferred embodiment, in Ila-IIb,
M is ruthenium (Ru), wolfram (W) or nickel (Ni);
m = 0 or 1, n = 0 or 1;
L 1 and L 2 each is chloride (CI " );
L is Ilia or Hid; wherein q, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 each is as defined above.
When n = 0, p = 0 or 1; when n = 1, p = 0;
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, C1-C15 alkoxy, C 6 -Ci5 aryloxy, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C 6 -Ci5 arylamino or C 2 -C15 heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl; Y is nitrogen, oxygen, CH, CH 2 , imino, C1-C15 alkoxy, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C3-C15 heteroaryl, C1-C15 alkylcarbonyl, C1-C15 alkoxycarbonyl, C 6 -Ci5 arylcarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylimino, C1-C15 alkylamino, C 6 -Ci5 arylamino or C 2 -Cis heterocyclic amino group; "Y— x" is either single bond or double bond;
When n = 0 and p = 1 , L 3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C 2 -Cis alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C1-C15 alkylcarbonyl, C 6 -Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C 6 -Ci5 arylaminocarbonyl, C1-C15 alkylamido, C 6 -Ci5 arylamido, C1-C15 alkylamino sulfonyl, C 6 -Ci5 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C 2 -Cis heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group. When n = 1 and p = 0, X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , C1-C15 alkyl, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C 2 -Cis heterocyclic aryl, C1-C15 alkylamino, C 6 -Ci5 arylamino or C 2 -Cis heterocyclic amino group.
In one more preferred embodiment of the present invention, wherein the structure Ila or lib:
When m = 0, Y is oxygen, nitrogen, carbonyl, imino, Ci-C 8 alkoxy, C 6 -Ci 2 aryloxy, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylimino, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -C 8 heterocyclic amino group;
When m = 1, X is oxygen, nitrogen, sulfur, CH, CH 2 , carbonyl; Y is nitrogen, oxygen, CH, CH 2 , imino, Ci-C 8 alkoxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, C 3 -Ci 2 heteroaryl, Ci-C 8 alkylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 arylcarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylimino, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -C 8 heterocyclic amino group; "Y— x" is either single bond or double bond;
When n = 0, p = 0 or 1; when n = 1, p = 0;
When n = 0 and p = 1 , L 3 is one or more substituted pyridine at the ortho-position, meta-position and/or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to the transition metal cation, wherein the substituents at the ortho-position, meta-position and/or para-position of pyridine are each selected from halogen, nitro, cyano, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, C 2 -C 8 alkenyloxy, Ci-C 8 silanyl, Ci-C 8 alkylsilyloxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, Ci-C 8 alkylcarbonyl, C 6 -Ci 2 arylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-Ci 2 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, Ci-C 8 alkylaminosulfonyl, C 6 -Ci 2 arylamino sulfonyl, Ci-C 8 sulfonylamido, C 3 -Ci 2 heteroaryl or C 2 -C 8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group;
When n = 1 and p = 0, X 1 and Y 1 are each oxygen, nitrogen, sulfur, carbonyl, imino, CH, CH 2 , Ci-C 8 alkyl, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, C 2 -Ci 2 heterocyclic aryl, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino or C 2 -C 8 heterocyclic amino group;
R 1 is H, Ci-Cs alkyl, C 2 -C 8 alkenyl, C 6 -C 12 aryl or C 6 -C 12 arylenyl; R 2 is methyl, ethyl, isopropyl, Ci-C 8 alkyl or C 6 -Ci 2 aryl;
E, E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are each independently selected from the group consisting of H, halogen atom, nitro, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, C 2 -C 8 alkenyloxy, Ci-C 8 silanyl, Ci-C 8 alkylsilyloxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, Ci-C 8 alkylcarbonyl, C 6 -Ci 2 arylcarbonyl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, Ci-C 8 alkylaminosulfonyl, C 6 -Ci 2 arylaminosulfonyl, Ci-C 8 sulfonylamido, C 3 -Ci 2 heteroaryl or C 2 -C 8 heterocyclic group; each optionally substituted with an alkyl, alkoxy, alkylthio, aryl, aryloxy, halogen atom or heterocyclic group..
In one most preferred embodiment of the present invention, wherein the structure
Ila or lib:
M is ruthenium;
L is Ilia or Hid; and in Ilia, q = 1, R 4 and R 5 each is 2,4,6-trimethylphenyl, R 6 and R 7 each is H; or in Hid, R 8 and R 9 each is cyclohexyl (Cy).
L 1 and L 2 each is chloride anion;
m = 0 or 1, and n = 0 or 1;
When m = 0, Y is CH 2 , H, C 1 -C4 alkoxy, Ci-C 4 alkylamino or C 6 -C 9 arylamino group;
When m = 1, X is nitrogen, Ci-C 3 alkylamino, CH, CH 2 , or carbonyl; Y is oxygen, nitrogen, imino, NH, Ci-C 4 alkyl, Ci-C 4 alkoxy, Ci-C 4 alkylamino, or C 6 -C 9 arylamino; "Y— X" is either single bond or double bond;
When n = 0, p = 0 or 1; when n = 1, p = 0.
When n = 0 and p = 1 , L 3 is one substituted pyridine at the meta-position or para-position, and the nitrogen atom of the substituted pyridine donates a pair of electron to ruthenium cation, wherein the substituents at the meta-position or para-position of pyridine are each selected from halogen, nitro, Ci-C 3 alkyl, Ci-C 3 alkoxy, Ci-C 6 alkylamino, unsubstituted or substituted C 6 -Ci 2 aryl;
When n = 1, X 1 is CH 2 , substituted or unsubstituted phenyl, or carbonyl; Y 1 is oxygen or carbonyl;
R 1 is H; when n = 1, R 2 is methyl, ethyl, or isopropyl; when n = 0, R 2 is H, halogen, C1-C4 alkyl or C1-C4 alkoxy in structure Ila.
E is H, halogen, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, Ci-C 8 alkylaminosulfonyl, C 6 -Ci 2 arylaminosulfonyl;
E 1 and E 2 are each H, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
E 3 is H;
E 4 is H or C 1 -C 4 alkyl;
E 5 and E 6 is H, halogen, C 1 -C 4 alkyl or Ci-C 6 alkoxy;
E 7 is H or C 1 -C 4 alkyl.
The third aspect, the present invention provides the following synthetic methods of making different kinds of transition metal complexes Ila-IIb.
Method 1 in Scheme 1 :
SM-2 (carbene intermediate) IV
3) Ligand la or lb Complex
(Z = CH 2 ) intermediate
(Va or Vb)
The intermediate of transition metal complex (Va or Vb) having the following structure:
Va Vb
(1) The carbene intermediate is prepared by the reaction of the tosylhydrazones SM-2 and NaOEt in anhydrous EtOH in a flask filled with inert gas (Ar); wherein, the sub stituents E and X 1 of SM-2 are each hydrogen, Ci-C 8 alkyl or Ci-C 8 alkoxy.
(2) The carbene intermediate prepared in step (1) is reacted with ML 1 L 2 (PPh 3 )3to obtain the complex intermediate IV in a flask filled with inert gas (Ar). (3) The complex intermediate obtained by step (2) is reacted with complex ligand la or lb to prepare another complex intermediate Va or Vb in a flask filled with inert gas (Ar); wherein, Va and Vb are compounds Ila or lib when L is PPh 3 ; M, L 1 , L 2 , Y, Y 1 , R 1 , R 2 , E, E 1 , E 2 and E 3 are each as defined above.
More preferred, L 1 and L 2 each is chloride anion (CI " ).
Wherein, in step (1), the preferred one of E and X 1 is hydrogen; the preferred usage of anhydrous organic solvent is 5-30 times weight of SM-2; the more preferred usage is 15 times; the preferred reaction temperature is 25-75 ° C, the more preferred temperature is 50-65 ° C .
In step (2), the preferred reaction temperature is -50 ° C to -85 ° C, the more preferred temperature is -60 ° C to -75 ° C ; the preferred usage of ML^Ls is 0.3-1.0 times molar ratio of SM-2, the more preferred usage is 0.6-0.7 times; the preferred compound of ML 1 !?! is RuCl 2 (PPh 3 ) 3 ;
In step (3) of method 1, the preferred reaction temperature is -50 ° C to -85 ° C, the more preferred temperature is -60 ° C to -75 ° C ; the preferred usage of complex ligand la or lb is 1-3 molar ratio of complex intermediate, the preferred usage is 1.5-2 eq.
When ML 1 !. 2 !, is RuCl PPh 3 ) 3 , the structure of product Va or Vb is as follows:
Va Vb
Method 2: the complex Va or Vb obtained by method 1 is reacted respectively with any electron-donating complex ligand L except PPh 3 to prepare following metal complexes Ila or lib, wherein, p = 0, q = 1, definition of M, L, L 1 , L 2 , Y, Y 1 , R 1 , R 2 , E, E 1 , E 2 and E 3 each is as defined above;
Ila lib
Wherein, the preferred one, in structure of transition metal complexs as the product Ila or lib, where a preferred ligand L is Ilia or Hid. The preferred reaction termperature is 20 ° C to 75 ° C, the more preferred reaction temperature reacted with complex ligand Ilia is 60 ° C to 75 ° C, the more preferred reaction temperature reacted with complex ligand Hid is 20 ° C to 35 ° C ; The preferred usage of Ilia or Hid is 1-3 times molar ratio of complex intermediate Va or Vb, the more preferred molar ratio is 1.5-2 eq;
Method 3: when L is PCy 3 or PPh 3 , the Ila or lib is reacted respectively with any electron-donating complex ligand L (Ilia) or L 3 to prepare the metal complex Ila or lib, wherein p = 0, M, L 1 , L 2 , Y, Y 1 , R 1 , R 2 , E, E 1 , E 2 , E 3 is each as defined above.
Method 4: when L is PCy 3 or Ilia, the Ila or lib is reacted respectively with any electron-donating complex ligand L 3 to prepare the metal complex Ila or lib, wherein p = 1, M, L 1 , L 2 , Y, Y 1 , R 1 , R 2 , E, E 1 , E 2 , E 3 is each as defined above. In method 4, the preferred reaction temperature is 20 ° C to 35 ° C .
From method 1 to method 4, L 1 and L 2 each is chloride anion.
In the present invention, when Z is CH 2 , the complex ligand la could be prepared by the following Suzuki reaction:
SM-1 la
When Z is CH 2 , another complex ligand lb could also be prepared by the above Suzuki reaction.
Wherein Y, Y 1 , R 1 , R 2 , E, E 1 , E 2 and E 3 each is as defined above. Based on currently developed technology, the metal complex Ila or lib of the present invention could also be prepared by the following two alternative procedures described in Schemes 2 & 3 :
Scheme 2:
1) NaOEt, EtOH
la or lb Va or Vb
(Z = TsNHN)
Ila or Hb Ila or lib
(L = PCy 3 ) I \
L = Mes-N N-Mes
T
(Mes = 2,4,6-trimethylphenyl)
In the above procedure, Z is TsNHN in structure la or lb.
In Scheme 2, la or lb reacts with NaOEt in anhydrous EtOH to form carbene in a flask filled with inert gas, followed by reacting with RuCl 2 P(Ph 3 ) 3 to form complex Va or Vb. The complex Va or Vb is reacted with Ilia or Hid effectively to obtain the complex Ila or lib in inert gas, respectively.
Scheme 3 :
CuCl, DCM
(L = PCy 3 or Mes— W ~ N-Mes
T
Complexes Ila and lib could also be prepared by the route in Scheme 3.
In Scheme 3, la or lb reacts with ruthenium complex 1 or 2 directly to form the desired complex Ila or lib in a flask filled with inert gas (Ar), respectively.
In the fourth aspect, the present invention provides a method of carrying out a metathesis reaction effectively with olefin substrate, comprising intramolecular ring-closing metathesis (RCM), intermolecular cross metathesis (CM) or ring-opening metathesis polymerization (ROMP) of cyclo-olefin substrate selectively in the presence of the novel ruthenium catalysts.
The preferred cyclo-olefin substrate for ROMP is optionally selected from dicyclopentadiene (DCPD), norbornene, cyclooctene, or a kind of tensional cycloolefin; each is optionally substituted or unsubstituted with one or more of F, CI, Br, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C2-C15 alkenyloxy, C1-C15 silanyl, C1-C15 alkylsilyloxy, C 6 -Ci5 aryl, C 6 -Ci5 aryloxy, C1-C15 alkylcarbonyl, C 6 -Ci5 arylcarbonyl, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C 6 -Ci5 arylaminocarbonyl, C1-C15 alkylamido, C 6 -Ci5 arylamido, C1-C15 alkylaminosulfonyl, C 6 -Ci5 arylaminosulfonyl, C1-C15 sulfonylamido, C3-C15 heteroaryl or C 2 -C15 heterocyclic group.
In one preferred embodiment of the present invention, wherein a kind of tensional cycloolefin substrates include the following structure Via- Vic:
Via VIb Vic
Wherein r = 1, 2, 3 or 4; s = 1, 2, 3 or 4;
A is O, S, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 aryloxy, d-C 15 alkylthio, d-C 15 alkoxycarbonyl, C1-C15 alkylamino, C 6 -Ci5 arylamino, C1-C15 alkylaminocarbonyl, C 6 -Ci5 arylaminocarbonyl, C1-C15 alkylamido, C 6 -Ci5 arylamido, or C1-C15 heterocyclic amido group;
G is a group of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomers or modified prodrugs;
R 10 and R 11 are each H, halogen, C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C 6 -Ci5 aryloxy, C 6 -Ci5 aryl, C2-C15 heterocyclic, C3-C15 heterocyclic aryl, C 1 -C 15 alkylcarbonyl, C 1 -C 15 alkyloxycarbonyl, C 6 -Ci 5 aryloxycarbonyl, C 1 -C 15 alkylaminocarbonyl, C 6 -Ci 5 arylaminocarbonyl, C 1 -C 15 alkylamido, C 1 -C 15 alkylsulfonyl, C 1 -C 15 alkylsulfonamido, liquid crystal monomer or modified pro-drug;
"Linker" is C1-C15 alkyl, C1-C15 alkoxy, C1-C15 alkylthio, C1-C15 alkylsilyoxy, C 6 -Ci5 aryloxy C 6 -Ci5 aryl, C1-C15 alkoxycarbonyl, C 6 -Ci5 aryloxycarbonyl, C1-C15 alkylaminocarbonyl, C 6 -Ci 5 arylaminocarbonyl, Ci-C 15 alkylamido, C 6 -Ci 5 arylamido, C1-C15 alkylsulfonamido, C 6 -Ci5 arylsulfonamido, C3-C15 heteroaryl or C2-C15 heterocyclic group.
In one more preferred embodiment of the present invention, wherein in structure Vla-VIc:
Wherein r = 1, 2, 3 or 4; s = 1, 2, 3 or 4;:
A is O, S, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 aryloxy, C 1 -C 15 alkylthio, Ci-C 8 alkoxycarbonyl, Ci-C 8 alkylamino, C 6 -Ci 2 arylamino, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, or Ci-C 8 heterocyclic amido group;
G is a kind of compounds with specific properties and uses; each is optionally selected from commercial liquid crystal monomers or modified prodrugs;
R 10 and R 11 are each H, halogen, Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, Ci-C 8 alkylsilyoxy, C 6 -Ci2 aryloxy, C 6 -Ci2 aryl, C2-Q heterocyclic, C3-C12 heterocyclic aryl, Ci-C 8 alkylcarbonyl, Ci-C 8 alkyloxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, Ci-C 8 alkylsulfonyl, Ci-C 8 alkylsulfonamido, liquid crystal monomer or modified pro-drug;
"Linker" is Ci-C 8 alkyl, Ci-C 8 alkoxy, Ci-C 8 alkylthio, Ci-C 8 alkylsilyoxy, C 6 -Ci 2 aryloxy, C 6 -Ci 2 aryl, Ci-C 8 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, Ci-C 8 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, Ci-C 8 alkylamido, C 6 -Ci 2 arylamido, Ci-C 8 alkylsulfonamido, C 6 -Ci2 arylsulfonamido, C3-C12 heteroaryl or C2-C 8 heterocyclic group.
In one most preferred embodiment of the present invention, wherein in structure Vla-VIc:
r = 1 or 2; s = lor 2;
A is O, CH 2 , C 1 -C5 alkyl-amino, C 1 -C5 alkoxy, C 1 -C5 alkylaminocarbonyl or C 1 -C5 heterocyclic amido group;
"Linker" is Ci-C 6 alkyl, C 1 -C5 alkoxy, C 1 -C5 alkylthio, C 1 -C5 alkoxycarbonyl, C 1 -C5 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, C 1 -C5 alkylamido or C 6 -Ci 2 arylamido group;
G is a kind of optionally modified prodrug of commercial drug Lipitor having the following structure VHa-VIId:
Vila Vllb VIIc Vlld
Wherein R 10 and R 11 are each H, C 1 -C5 alkoxy, C 6 -Ci 2 aryloxy, C 1 -C5 alkoxycarbonyl, C 6 -Ci 2 aryloxycarbonyl, C 1 -C5 alkylaminocarbonyl, C 6 -Ci 2 arylaminocarbonyl, C 1 -C5 alkylamido, C 6 -Ci 2 arylamido, liquid crystal monomer or modified pro-drug;
R 12 is cyclopropyl, Ci-C 6 alkly, C3-C 6 cycloalkyl, Ci-C 6 alkoxy, C 6 -Ci 2 aryl, C 6 -Ci 2 aryloxy, Ci-C 6 alkylamino, C 6 -Ci 2 arylamino, Ci-C 6 alkylsulfonamido, C 6 -Ci 2 arylsulfonamido, C 3 -Ci 2 heterocyclic aryl or C 2 -C 6 heterocyclic group.
In another preferred embodiment, the present invention provides a method of making a quality-modified polymer having the following structure Villa- Vlllb in the presence of one or two more mixed ruthenium catalysts;
Villa Vlllb (PDCPD)
The present invention provides a process of preparing functional polymers Villa- Vlllb in the presence of one or two more mixed catalysts.
The present invention also provides a useful method of making functional polymers, comprising reacting one or more monomers in the presence of the novel ruthenium catalysts.
In the fifth aspect, the present invention provides a composition of comprising a modified prodrug or functional group G having the following structure IXa-IXc:
IXa IXb
Wherein: r = 1, 2, 3 or 4; s = 1, 2, 3 or 4;
A, G, "Linker", R 11 and R 12 each is as defined above.
In the most preferred embodiment of the present invention, wherein a modified prodrug or functional group G having the following structures IXa-IXc:
r =1 or 2; s =1 or 2;
A, "Linker", R 10 and R 11 each is as defined above;
G is a kind of optionally modified pro-drug of Lipitor having the following structure VHa-VIId:
Vila VI lb VIIc Vlld
Wherein R 12 is cyclopropyl, C 1 -C5 alkly, C3-C 6 cycloalkyl, C 1 -C5 alkoxy, C 6 -Ci 2 aryl, C 6 -Ci2 aryloxy, C1-C5 alkylamino, C 6 -Ci2 arylamino, C1-C5 alkylsulfonamido, C 6 -Ci 2 arylsulfonamido, C3-C 12 heterocyclic aryl or C 2 -C 6 heterocyclic group.
The present invention relates to two classes of novel carbene ligands and ruthenium complexes as catalysts in uses of carrying out metathesis reactions effectively e.g., preparation of the high strength and/or stiffness polymer materials, functional polymers linked with small molecule pro-drugs and liquid crystal materials.
Currently, the present invention provides the following significant achievements:
1. Two classes of novel carbene ligands and ruthenium complexes have been designed and prepared; and the electronic and steric effect of different substituted ligands on the catalytic activity and stability of various Ru complexes have been investigated. It is determined that some of novel Ru catalysts in the present invention have much better catalytic selectivity and variable physical diversity than Grubbs and Hoveyda catalysts in the ROMP and RCM reactions.
2. The experimental results show that some of novel Ru catalysts in the present invention have high activity and selectivity for different olefin ROMP and RCM reactions, so the invention provides a useful synthetic method of carrying out olefin metathesis reactions effectively in preparation of polymer materials and pharmaceutical intermediates.
3. The present invention provides several developed methods for preparation of carbene ligands and Ru catalysts at lower cost, and it also provides some efficient methods for preparation of various functional polymer materials with different chemical and physical properties.
4. The present invention provides several developed processes of conducting ROMP reaction with one or two more mixed of novel active Ru catalysts for preparation of the high-strength polymer materials and some functional polymers linked with small molecule pro-drugs and/or liquid crystal materials.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 : Single-crystal X-ray Structure of Ru Catalyst 8m.
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises two novel classes of carbene ligands and ruthenium complexes as catalysts for metathesis reactions. To study the electronic and steric effects of multi- substituted benzylidene ligands on the stability and activity of Ru complexes, based on the following reported procedure in Schemes 1-3, different kinds of the complex ligands (3a-3bf, 5a- 5j, 7a-7r, 9a-9j) have been prepared and reacted with the Ru complex 1 to obtain different kinds of new Ru complex (4a-4bf, 6a-6j, 8a-8r, lOa-lOj, lla-llr). During preparation and activity evaluation of various Ru complexes with various substituted 2-aminobenzylidene ligands in the following Schemes 4-8, different kinds of the electron-withdrawing and/or electron-donating effect and steric effect on the stability and selective activity for ROMP and RCM reactions have been found as shown in Schemes 9-16 and Tables 1-6.
Significant electronic effect of various substituted benzylidene ligands on the stability of Ru complexes: Based on different described synthetic methods and procedures in Schemes 1-3, there are different kinds of new olefin or carbene ligands (Ia-Ib) and Ru complexes (Ila-IIb) prepared in the present invention. Moreover, significant substituent effect of different substituted benzylidene ligands on the stability and activity of Ru complexes has been observed and developed selectively for ROMP and RCM reactions, and some novel Ru catalysts have been prepared much more active and selective than prior reported Ru catalysts for different kinds of ROMP and RCM reactions.
According to previously described synthetic methods, various new Ru complexes 4a-4bf have been prepared by the reaction listed in Scheme 4, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 4:
-NL
(Mes = 2,4,6-trimethylb r,N- Mes
enzene)
3a-3ay 4a-4bf
Some selected structure of prepared ruthenium complexes 4a-4bf (la: Cy cyclohexyl, lb = 2,4,6-trimethylbenzene) is listed as follows:
4ba 4bb 4bc
4bd 4be 4bf
According to previously described synthetic methods, various new Ru complexes 6a-6j have been prepared by the reaction listed in Scheme 5, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 5:
Some selected structure of prepared ruthenium complexes 6a-6j (la: Cy cyclohexyl, lb = 2,4,6,- trimethylbenzene) is listed as follows:
6g 6h 6j (Unstable)
According to previously described synthetic methods, various new Ru complexes 8a-8r have been prepared by the reaction listed in Scheme 6, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 6:
7a-7r (Mes = 2,4,6-trimethylphenyl) 8a-8r Some selected structure of prepared ruthenium complexes 8a-8r (la: Cy cyclohexyl, lb = 2,4,6,- trimethylbenzene) is listed as follows:
8(1 8e (Unstable) 8f (Unstable)
8g 8h 8j
The structure of Ru catalyst 8m is confirmed by single-crystal X-ray as shown in Figure 1.
According to previously described synthetic methods, various new Ru complexes lOa-lOj have been prepared by the reaction listed in Scheme 7, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively. Scheme 7:
9a-9j (Mes = 2,4,6-trimethylbenzene) lOa-lOj
Some selected structure of prepared ruthenium complexes lOa-lOj (la: cyclohexyl, lb = 2,4,6,- trimethylbenzene) is listed as follows:
(Unstable) (Unstable)
lOd lOe lOf
lOg lOh 10j
According to previously described synthetic methods, various new Ru complexes lla-llr have been prepared by the reaction listed in Scheme 8, and the corresponding metathesis activity of each Ru complex has been studied for RCM and ROMP reactions with different olefin substrates, respectively.
Scheme 8:
Ru catalyst (lib) 11 (Ru catalyst lib)
(n = 0, p = 0) (n = 0, p = l)
Some selected structure of prepared ruthenium complexes lla-llr (la: Cy = cyclohexyl, lb = 2,4,6,- trimethylbenzene) is listed as follows:
11 a 11 b 11 c
n 11 h
11 p 11 q 11 r
Two alternative production procedures for preparation of some highly active metathesis catalysts: In order to prepare different kinds of Ru catalyst at lower cost, based on some references (Zhan et al, US20070043180A1 and WO2007003135A1) and new process development as described in Schemes 9 and 10, there is the following alternative procedure developed in Scheme 9 for scale-up production of different Ru catalysts in the present invention.
llh
Scheme 9: A convenient route for preparation of some Ru complexes In Scheme 9, the starting material 4-SM was reacted with sodium ethoxide to produce carbene intermediate 4-1 first, followed by reacting with RuCl 2 (PPh 3 ) 3 directly to form Ru complex intermediate 4-2. The triphenylphosphine ligand (PPh 3 ) of Ru intermediate 4-2 was replaced by another ligand PCy 3 (4-3) to form a new Ru complex 4i. The phosphine ligand of Ru intermediate 4-2 or 4i was further replaced by an HC ligand (H 2 IMes, 4-4) to form another Ru complex 4j . The Ru complex 4j could directly react with another ligand 4-chloro pyridine (4-5) to make the Ru complex llh.
Scheme 10: A convenient route for preparation of some Ru complexes In Scheme 10, the Ru complex (Zhan Catalyst 2b) could directly react with a ligand 5h to form the desired Ru complex 6h in good yield.
So far, to study the relative activity and catalytic selectivity of above prepared catalysts 4a-4bf, 6a-6j, 8a-8r, lOa-lOj, and lla-llr, two olefin substrates 15 and 17 in Equations 1 and 2 were chosen for RCM reactions, and different kinds of cyclic olefin substrates 19, 21, 23, 25, 27, 29 and 31 in Equations 3-9 were selected for ROMP reactions, and the kinetic results of different conducted RCM and ROMP reactions for each new catalyst are listed in Tables 1, 2, 3, 4 and 5, respectively. Other eight prior known Ru catalysts la-lb and 2a-2f listed in Scheme 1 are also selected for evaluation of metathesis activity study with various substrates 15, 17, 19, 21, 23, 25, 27, 29 and 31 in comparison to all new Ru catalysts in the present invention.
The evaluation of catalytic activity for RCM in Equation 1 with different catalysts 4a-4bf, 6a-6j, 8a-8r, lOa-lOj, and lla-llr has been done under the same reaction condition, and the valuable experimental data for different Ru catalysts are selected and listed in Tables 1-1 to 1-4, respectively.
Equation
15 16
Table 1-1 : Activity Results of Some Selected Complexes 4a-4bf for Substrate 15
Conversion (% by HPLC)
Entry Catalyst
10 min 30 min 1.5 hr 3.0 hr
1 4a 40 81 98
2 4b 52 85 98
3 4f 84 94 96 100 4 4g 94 100
5 4u 96 100
6 4v 41 71 93 100 7 4y 43 66 87 94 8 4aa 21 59 82 92 9 4ab 94 100 10 4ac 70 90 100
11 4af 93 97
12 4aj 95 99
13 4ap 71 82 93 98
14 4at 24 48 73 100
15 4ba 62 73 79 85
16 4bb 100
17 4bc 94 100
18 4bd 68 81 84 89
19 4be 100
Among Ru complexes 4a-4bf, only some of new complexes (such as 4f, 4g, 4u, 4ab, 4aj, 4bb and 4be) show high catalytic activity, the rest of them not listed in Table 1-1 have lower or very poor activities for RCM reaction. Based on the determined results in Table 1-1, the activity of Ru complexes 4a-4bf for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 3a-3bf. However, some of complexes 4a-4bf non-active for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
Table 1-2. Activity Results of Some Selected Complexes 6a-6j for Substrate 15
10 min 30 min 1.5 hr 3.0 hr
1 6e 0 0 0 0
2 6h 95 100
3 6j 45 70 89 95
4 2e 0 0 0 0
Among complexes 6a-6j, only a Ru complexes 6h shows high catalytic activity and much better than the known catalyst 2e, the rest of them not listed in Table 1-2 have worse or very poor activities. Based on the determined results in Table 1-2, the activity of Ru complexes 6a-6j for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 5a-5j. However, some of complexes 6a-6j non-active for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
Table 1-3. Activity Results of Some Selected Complexes 8a-8r for Substrate 15 Conversion (% by HPLC)
Catalyst
lO min 30 min 1.5 hr 3.0 hr
1 8b 73 79 98
2 8g 0 0 0 0
3 8h 96 98 99
4 8q 53 76 88 99
5 8r 79 93 100
6 2c 47 69 82 92
Among complexes 8a-8r, only a few complexes (such as 8b, 8h and 8r) show good catalytic activity and much better than the known catalyst 2c, the rest of them not listed in Table 1-3 have worse or very poor activities. Based on the determined results in Table 1-3, the activity of Ru complexes 8a-8r for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 7a-7r. However, some of non-active complexes 8a-8r for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
Table 1-4: Activity Results of Some Selected Complexes lOa-lOj for Substrate 15
Conversion (% by HPLC)
Entry Catalyst
10 min 30 min 1.5 hr 3.0 hr
1 10c 90 99
2 lOd 96 100
3 lOe 91 96 100
4 lOg 84 99
5 10j 86 92 99
6 2d 62 78 90 98
Among complexes lOa-lOj, several complexes (such as 10c, lOd, lOe and lOg) show good or high catalytic activity and much better than the known catalyst 2d, the rest of them not listed in Table 1-4 have worse or very poor activities. Based on the determined results in Table 1-4, the activity of Ru complexes lOa-lOj for RCM is significantly affected by the electronic and steric effect of different substituents incorporated in various new ligands 9a-9j. However, some of non-active complexes 10a- lOj for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity. Table 1-5: Activity Results of Some Selected Complexes lla-llr for Substrate 15
Conversion (% by HPLC)
Entry Catalyst
10 min 30 min 1.5 hr 3.0 hr
1 lib 38 57 60 61
2 lie 44 57 65 68
3 lip 39 43 45 45
4 llq 32 34 38 40
Among complexes lla-llr, only a few complexes (such as 11c, lie and lip) show lower catalytic activity, the rest of them not listed in Table 1-5 have worse or very poor activities. Based on the determined results in Table 1-5, the activity of Ru complexes lla-llr for RCM is significantly affected by the electronic effect of different substituented pyridine ligands. However, some of complexes lla-llr non-active for RCM can be used effectively in the following ROMP (Equations 3-9) with high activity and selectivity.
In order to find some new catalysts with better activity and selectivity, it is designed to carry out a RCM reaction with a phenyl-substituted diene substrate 17 as shown in Equation 2 instead of unsubstituted diene substrate 15 for further evaluation of some active catalysts selected from the catalysts 4a-4bf, 6a-6j, 8a-8r, lOa-lOj, and lla-llr according to activity results in Tables 1-1 to 1-5. The experimental results of RCM activity for substrate 17 are listed in Tables 2.
Equati
17 18
Table 2: Activity Results of Some Selected Ru Complexes for Substrate 17
Conversion (% by HPLC)
Entry Catalyst
10 min 30 min 1.5 hr 3.0 hr
1 4f 67 86 94 99
2 4g 61 78 86 98
5 4ab 63 85 96 99 6 4ad 51 68 79 95
7 4af 72 86 92 99
8 4be 49 73 86 91
9 6h 70 88 90 96
10 8h 75 88 96 99
11 10a 42 65 81 98
12 10c 71 82 85 92
13 lOd 82 94 95 100
14 lOf 35 63 83 99
15 lOg 46 69 84 100
To develop more effective ROMP catalysts and prepare better quality of new functional polymers, and also better to measure the difference of various active Ru catalysts, the evaluation of catalytic activity for different ROMP reactions in Equations 3-9 with different catalysts 4a-4bf, 6a-6j, 8a-8r, lOa-lOj, and lla-llr has been done under the same reaction condition, and some valuable results for different Ru catalysts are selected or listed in Tables 3 to 6, respectively. Based on the broad test, it is useful to find some active and selective catalysts for ROMP and RCM reactions, respectively.
Equation 3 :
19 20
After screening with most of new Ru catalysts, it is found that some catalysts such as 8g and 8m could selectively catalyze the ROMP reaction effectively.
Equation 4:
Ru catalyst
(0.1% molar)
21 22
After screening with most of new Ru catalysts, it is found that some catalysts such as 4d and 8j could catalyze the ROMP reaction effectively.
Equation 5 :
(0.1% molar)
23 24
The ROMP results show that the catalysts 4b, 4f, 4v, 4y, 4aa, 8b and 8h of the present invention have better activity and selectivity for norbornene (23) polymerization. Catalytic polymerization was completed in 10-60 min, and the polymer product (24) has better tensile-strength when it is prepared as film.
Equation 6:
The ROMP results show that the catalysts 4b, 4f, 4v, 4y, 4aa, 4ag, 4ar, 4au, 8a, 8b, 8c, 8h, 8m and 8q of the present invention have better activity and selectivity for DCPD (25) polymerization. The ROMP polymerization was completed in 5-60 min for different Ru catalysts. The reaction temperature is preferred to be 40-60 ° C . By using one or two more mixed catalysts, it is surprised to obtain the high strength and high stiffness polymer PDCPD.
The property tests of various PDCPD (26) samples in the present invention show that several PDCPD products have more better tensile strength (55-62Mpa) and flexural strength (78-83Mpa) than those of commercial PDCPD products such as "Pentam, Metton, and Prometa" (tensile strength: 40-50Mpa, and flexural strength: 66-75Mpa) reported by other companies prepared with their own ROMP catalysts in Japan and USA, which advantage in the present invention will provide an alternative method of making high-quality of PDCPD material for broad uses in polymer industry.
Equation 7:
27 28
Some selected structure of prepared polymers 28a-28g is listed as follows, and ROMP results are listed in Table 3 :
28e 28f 28g Table 3 : Selected ROMP results
The results of Table 3 show that, small molecule liquid crystal or pro-drug monomer can react with new Ru catalysts selected from the present invention to form polymerized macromolecule liquid crystal (28c and 28d) and polymer-linked prodrugs (28e, 28f and 28g) with special properties and applications. The results of activity test show that several new catalysts (such as 4d, 4f, 6g and 11a) of the present invention have better catalytic activity for olefin monomers (27a-27g), and the ROMP reactions were completed in 5-15 hrs. Yield is better than 80% with optimized polymerization conditions in the presence of new Ru catalyst 4d.
The results of polymerization test show that different Ru catalysts of the present invention have significantly different activity and selectivity for different cyclo-olefin monomers. In particular, some new Ru catalysts (e.g., 4d and 6g) have lower catalytic activities in RCM reaction, but have very good activity in ROMP reactions, which demonstrates that several new Ru catalysts in the present invention have the high selectivity and catalytic activity for ROMP and RCM, respectively.
40 Table 4: Selected ROMP results
The results in Table 4 show that most of cyclo-olefin monomers with different functional groups (29a-29n) were polymerized in the presence of new Ru catalysts such as 4d or 6g selected from the present invention to form functional polymers with different chemical and physical properties.
Equation 9:
Some selected structure of prepared polymers 32a-32m is listed as follows, and some selected ROMP results are listed in Table 5 :
32a 32b 32c 32d
32e 32f 32g 32h
32i 32j 32k 32m
Table 5 : Selected ROMP results
The results in Table 5 show that hat most of cyclo-olefin monomers with different functional groups (31a-31m) were polymerized in the presence of new Ru catalyst 4d selected from the present invention to form functional polymers with different chemical and physical properties. Moreover, several products 32a, 32b, 32c, and 34m could be used to form film with high strength (over 50 Mpa).
Based on the activity studies in equations 1-9 and Tables (1-1, 1-2, 1-3, 1-4, 1-5 and 2), it is found that some of novel Ru catalysts such as 4d, 4f, 4g, 4ab, 6g, 6h, 8g, 8h, 10c and lOd have much better activity and selectivity than other tested and reported metathesis catalysts for the ROMP and RCM reactions, respectively. Moreover, it is found that the electronic effect of multi- substituted benzylidene ligands on the activity and selectivity of Ru complexes is one of the most important factors for the development of new active and selective metathesis catalysts for ROMP and RCM reactions. Based on the intensive study, the present invention provides some useful methods of carrying out either ROMP or RCM reaction with one or two more mixed of novel active Ru catalysts for preparation of some functional polymers linked with small molecule prodrugs and/or pharmaceutical intermediates, respectively.
EXAMPLES
General: Infrared (IR) spectra were recorded on a Fourier Transform AVATAR™ 360 E.S.P™ spectrophotometer (Unit: cm "1 ). Bands are characterized as broad (br), strong (s), medium (m), and weak (w). 1H NMR spectra were recorded on a Varian-400 (400 MHz) spectrometer. Chemical shifts are reported in ppm from tetramethylsilane with the solvent resonance as the internal standard (CDC1 3 : 7.26 ppm). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, br = broad, m = multiplet), coupling constants (Hz), integration, and assignment. 19 F and 31 P NMR spectra were recorded on a Varian-400 (400 MHz) and Gemini-2000 (300MHz) spectrometers. The chemical shifts of the fluoro resonances were determined relative to trifluoroacetic acid as the external standard (CF 3 CO 2 H: 0.00 ppm), and the chemical shifts of the phosphorus resonances were determined relative to phosphoric acid as the external standard (H 3 PO 4 : 0.00 ppm). Mass spectra were obtained at Thermo Finnigan LCQ Advantage. Unless otherwise noted, all reactions were conducted in oven- (135°C) and flame-dried glassware with vacuum-line techniques under an inert atmosphere of dry Ar. THF and Et 2 0 were distilled from sodium metal dried flask, DCM, pentane, and hexanes were distilled from calcium hydride. Different substituted 2-alkoxystyrene ligands were prepared according to literature procedures as shown in Schemes 1-3. Most chemicals were obtained from commercial sources and confirmed to be used without any quality problems. All product purification was performed with silica gel 60 (200-400 mesh) obtained from Qingdao Haiyang Chemical Co. General procedures for preparation of different Ru complexes are described in examples 1 and 2, respectively. General procedures for evaluation of the RCM and ROMP reactions are described in examples 104-107, respectively.
Example 1
Synthesis of Ru complex 4a
(H 2 IMes)(PCy 3 )Cl 2 Ru=CHPh (formula lb, 860mg, l .Ommol) and CuCl (270 mg, 2.5mmol, 2.5 eq) were added into a 100 mL of two-neck round-bottom flask filled with inert gas (Ar), and followed by adding DCM (15 mL) and ligand 3a (250 mg, 1.2mmol, 1.2 eq) into the DCM solution at 20-25°C. The reaction was stirred until completed in 30-60 min. (monitored by TLC). The reaction mixture was filtered and concentrated, then purified by flash column eluting with a gradient solvent (Pentane/DCM 2/1 to DCM). The purified solid product was washed with methanol, and dried under vacuum to obtain 27mg of green solid product 4a, yield: 4%. The green product was confirmed by 1 HNMR. Ru complex (4a) 1 HNMR (400 MHz, CDC1 3 ): δ 19.09 (s, lH, Ru=CH),
7.51-6.70 (m, 13H), 5.31 (m, 1H), 4.30 (d, J = 12.9 Hz, 1H), 4.04 (s, 4H, NCH 2 CH 2 N), 3.61 (d, J= 12.9 Hz, 1H), 2.45 (s, 12H), 2.33 (s, 6H).
Example 2 Synthesis of Ru complex 4b
(PCy 3 ) 2 Cl 2 Ru=CHPh (formula la, 830mg, l .Ommol) and CuCl (270 mg, 2.5mmol, 2.5 eq) were added into a 100 mL of two-neck round-bottom flask filled with inert gas (Ar), and followed by adding DCM (15 mL) and ligand 3b (250 mg, 1.2mmol, 1.2 eq) into the DCM solution at 20-25°C. The reaction was stirred until completed in 30-60 min. (monitored by TLC). The reaction mixture was filtered and concentrated, then purified by flash column eluting with a gradient solvent (Pentane/DCM 2/1 to DCM). The purified solid product was washed with methanol, and dried under vacuum to obtain 195mg of green solid product 4b, yield: 29%. The green product was confirmed by 1 HNMR.
Ru complex (4b) 1 HNMR (400 MHz, CDC1 3 ): δ 19.31 (d, J = 8.4 Hz, Ru=CH), 7.57-7.50 (m, 4H), 7.31-7.29 (m, 1H), 7.15 (d, J = 5.6 Hz, 1H), 6.84-6.81 (m, 2H), 5.78 (d, J = 12.0 Hz, 1H), 3.71 (s, 3H), 3.62 (d, J = 12.0 Hz, 1H), 2.51 (s, 3H), 2.22-1.13 (m, 33H, PCy 3 ).
Example 3
Synthesis of Ru complex 4c
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 35 mg of green solid product 4c was obtained (yield: 5%).
Ru complex (4c) 1 HNMR (400 MHz): δ 19.09 (s, lH, Ru=CH), 7.50-6.69 (m,
12H), 5.27 (m, 1H), 4.33 (d, J = 12.9 Hz, 1H), 4.04 (s, 4H, NCH 2 CH 2 N), 3.59 (d, J = 12.9 Hz, 1H), 2.45 (s, 12H), 2.37 (s, 6H).
Example 4
Synthesis of Ru complex 4d
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 231 mg of green solid product 4d was obtained (yield: 32%).
Ru complex (4d) 1 HNMR (400 MHz, CDC1 3 ): δ 18.68 (s, Ru=CH), 7.23-6.65 (m, 10H), 6.36 (dd, J = 2.8, 9.6 Hz, 1H), 6.03 (d, J = 12.8 Hz, 1H), 4.14-3.90 (m, 4H, NCH 2 CH 2 N), 3.85 (s, 3H), 3.47 (d, J= 12.8 Hz, 1H), 2.89-1.62 (m, 18H). Example 5
Synthesis of Ru complex 4e
The synthetic procedure is the same as in Example 2 in 1.0 mmol scale. 243 mg of green solid product 4e was obtained (35% yield).
Ru complex (4e) 1 HNMR (400 MHz, CDC1 3 ): δ 19.28 (d, J = 8.4 Hz, Ru=CH), 7.45 (d, J = 8.8 Hz, 2H), 7.31-7.16 (m, 3H), 6.83 (d, J = 8.8 Hz, 2H), 5.13 (t, J = 12.4 Hz, 1H), 7.96 (d, J = 12.4 Hz, 1H), 3.85 (d, J = 12.4 Hz, 1H), 3.80 (s, 3H), 2.28-1.24 (m, 33H, PCy 3 ).
Example 6
Synthesis of Ru complex 4f
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 103 mg of green solid product 4f was obtained (yield: 14%).
Ru complex (4f) 1 HNMR (400 MHz, CDC1 3 ): δ 18.99 (s, Ru=CH), 7.48-7.44 (m, 1H), 7.19-6.86 (m, 7H), 6.72-6.66 (m, 1H), 5.29 (t, J = 13.2 Hz, 1H), 4.19-3.58 (m, 8H), 2.52-2.37 (m, 18H).
Example 7
Synthesis of Ru complex 4g
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 61 mg of green solid product 4g was obtained (yield: 8%).
Ru complex (4g) 1 HNMR (400 MHz, CDC1 3 ): δ 19.11 (s, lH, Ru=CH), 8.36 (dd, J = 2.0, 8.0 Hz, 1H), 7.29-6.65 (m, 10H ), 5.30 (t, J = 13.6 Hz, 1H), 4.23 (d, J = 13.2 Hz, 1H), 4.10 (s, 3H), 3.80 (s, 4H, NCH 2 CH 2 N), 3.69 (d, J = 13.2 Hz, 1H), 2.65-2.08 (m, 18H).
Example 8
Synthesis of Ru complex 4h
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 315 mg of green solid product 4h was obtained (yield: 42%).
Ru complex (4h) 1 HNMR (400 MHz, CDC1 3 ): 19.02 (s, 1H, Ru=CH), 7.21-6.82 (m, 8H), 6.40 (dd, J = 9.6 Hz, 1.6 Hz), 5.21 (m, 1H), 4.06-4.00 (m, 5H), 3.70 (s, 3H), 3.54 (d, J= 13.2 Hz, 1H), 2.48-2.18 (m, 24H).
Example 9
Synthesis of Ru complex 4j
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 353 mg of green solid product 4j was obtained (yield: 48%).
Ru complex (4j) 1H- MR (400 MHz, CDC1 3 ): δ 18.88 (s, lH, Ru=CH), 7.57-6.44 (m, 11H), 5.36 (t, J = 13.2 Hz, 1H), 4.16-4.02 (m, 5H), 4.01 (d, J = 13.2 Hz, 1H), 2.75-2.00 (m, 19H), 1.01-0.90 (m, 6H).
Example 10
Synthesis of Ru complex 4k
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 490 mg of green solid product 4k was obtained (yield: 68%).
Ru complex (4k) 1 HNMR (400 MHz, CDC1 3 ): δ 18.90 (s, 1H, Ru=CH), 7.27-6.77 (m, 9H), 6.41 (d, J = 8.0 Hz, 1H), 5.43 (t, J = 13.2 Hz, 1H), 4.18-4.00 (m, 5H), 3.25 (d, J = 13.6 Hz, 1H), 2.76-1.27 (m, 24H).
Example 11
Synthesis of Ru complex 4m
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 404 mg of green solid product 4m was obtained (yield: 52%).
Ru complex (4m) 1 HNMR (400 MHz, CDC1 3 ): δ 18.95 (s, lH, Ru=CH), 7.43-6.36 (m, 10H), 4.00 (m, 6H), 2.67-2.06 (m, 20H), 0.90-0.83 (m, 12H).
Example 12
Synthesis of Ru complex 4n The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 470 mg of green solid product 4n was obtained (yield: 64%).
Ru complex (4n): 1H- MR (400 MHz, CDC1 3 ): δ 18.88 (s, lH, Ru=CH), 7.25-6.36 (m, 9H), 5.40 (t, J= 13.2 Hz, 1H), 4.14-4.00 (m, 6H), 2.77-1.90 (m, 27H).
Example 13
Synthesis of Ru complex 4p
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 184 mg of green solid product 4p was obtained (yield: 26%).
Ru complex (4p) 1 HNMR (400 MHz, CDC1 3 ): δ 18.91 (s, lH, Ru=CH), 7.63-6.42
(m, 10H), 5.27 (t, J = 13.2 Hz, 1H), 4.13-4.01 (m, 5H), 3.44 (d, J = 13.2 Hz, 1H), 2.46-2.00 (m, 21H).
Example 14
Synthesis of Ru complex 4q
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 291 mg of green solid product 4q was obtained (yield: 38%).
Ru complex (4q) 1 HNMR (400 MHz, CDC1 3 ): δ 18.75 (s, lH, Ru=CH), 7.26-6.21 (m, 9H), 4.05-3.85 (m, 5H), 3.72 (s, 3H), 3.34 (d, J = 13.2 Hz, 1H), 2.82-0.95 (m, 30H).
Example 15
Synthesis of Ru complex 4r
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 101 mg of green solid product 4r was obtained (yield: 14%).
Ru complex (4r) 1 HNMR (400 MHz, CDC1 3 ): δ 18.89 (s, lH, Ru=CH), 7.69-6.43 (m, 10H), 5.23 (dd, J = 13.2, 11.3 Hz, 1H), 4.16-3.94 (m, 5H), 3.46 (d, J = 11.3 Hz, 1H), 2.62-1.00 (m, 21H).
Example 16 Synthesis of Ru complex 4s
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 679 mg of green solid product 4s was obtained (yield: 85%).
Ru complex (4s) 1 HNMR (400 MHz, CDC1 3 ): δ 18.68 (s, lH, Ru=CH), 7.28-6.42 (m, 10H), 6.37 (d, J= 8.5 Hz, 1H), 5.05 (m, 1H), 4.06-3.93 (m, 7H,), 3.57 (d, J= 12.8 Hz, 1H), 2.89-1.29 (m, 29H).
Example 17
Synthesis of Ru complex 4t
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 185 mg of green solid product 4t was obtained (yield: 23%).
Ru complex (4t) 1 HNMR (300 MHz, CDC13): δ 18.97 (s, lH, Ru=CH), 8.54-8.45 (m, 2H), 6.66-6.96 (m, 8H), 4.16-4.10 (m, 1H), 4.03 (s, 4H, NCH 2 CH 2 N), 2.63-1.75 (m, 22H), 0.92 (d, J= 7.6Hz), 0.83 (d, J= 7.6Hz).
Example 18
Synthesis of Ru complex 4u
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 254 mg of green solid product 4u was obtained (yield: 32%).
Ru complex (4u) 1 HNMR (300 MHz, CDC13): δ 19.03 (s, lH, Ru=CH), 7.48-6.63 (m, 10H), 5.53 (m, 1H), 4.81-4.78 (m, 1H), 4.00 (s, 4H, NCH 2 CH 2 N), 2.51-2.49 (m, 1H), 2.51-2.32 (m, 18H), 1.12 (d, J= 7.6Hz), 1.04 (d, J= 7.6Hz).
Example 19
Synthesis of Ru complex 4v
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 73 mg of green solid product 4v was obtained (yield: 10%).
Ru complex (4v) 1 HNMR (400 MHz, CDC1 3 ): δ 18.97 (s, Ru=CH), 7.50-6.58 (m, 11H), 5.26-3.52 (m, 8H), 3.48-2.07 (m, 18H), 1.23 (d, J= 6.4 Hz, 6H). Example 20
Synthesis of Ru complex 4w
The synthetic procedure is the same as in Example 2 in 1.0 mmol scale. 219 mg of green solid product 4w was obtained (yield: 31%).
Ru complex (4w) 1 HNMR (400 MHz, CDC1 3 ): δ 19.56 (d, J = 9.9 Hz, Ru=CH),
8.20 (d, J= 8.1 Hz, 1H), 7.66-6.84 (m, 6H), 5.46 (d, J= 12 Hz, 1H), 5.22 (t, J= 6 Hz, 1H), 4.56 (m, 1H), 3.95 (d, J= 12.0 Hz, 1H), 2.34-0.87 (m, 39H, PCy 3 ).
Example 21
Synthesis of Ru complex 4x
The synthetic procedure is the same as in Example 2 in 1.0 mmol scale. 420 mg of green solid product 4x was obtained (yield: 58%).
Ru complex (4x) 1 HNMR (400 MHz, CDC1 3 ): δ 19.55 (d, J = 9.9 Hz, Ru=CH), 8.14 (d, J = 8.1 Hz, 1H), 7.36-6.83 (m, 6H), 5.46 (d, J = 12.0 Hz, 1H), 5.13 (t, J = 6.0 Hz, 1H), 4.56 (m, 1H), 3.90 (d, J= 12.0 Hz, 1H), 2.30-1.25 (m, 39H, PCy 3 ).
Example 22
Synthesis of Ru complex 4y
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 267 mg of green solid product 4y was obtained (yield: 37%).
Ru complex (4y): 1 HNMR (400 MHz, CDC1 3 ): δ 18.83 (s, Ru=CH), 7.50-6.39 (m, 11H), 5.21 (t, J= 12.4 Hz, 1H), 4.69-3.46 (m, 9H), 2.62-2.08 (m, 18H).
Example 23
Synthesis of Ru complex 4z
The synthetic procedure is the same as in Example 2 in 1.0 mmol scale. 362 mg of green solid product 4z was obtained (yield: 52%).
Ru complex (4z) 1 HNMR (400 MHz, CDC1 3 ): δ 19.35 (d, J = 9.9 Hz, Ru=CH), 8.11 (d, J = 8.1 Hz, 1H), 7.34-6.85 (m, 6H), 5.48 (d, J = 12.0 Hz, 1H), 5.27 (t, J = 6 Hz, 1H), 3.93 (d, J= 12.0 Hz, 1H), 3.88 (s, 3H), 2.33-1.24 (m, 33H, PCy 3 ). Example 24
Synthesis of Ru complex 4aa
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 631 mg of green solid product 4aa was obtained (yield: 84%).
Ru complex (4aa) 1 HNMR (400 MHz, CDC1 3 ): δ 18.89 (s, Ru=CH), 7.60-6.45 (m, 11H), 5.13-3.52 (m, 8H), 2.95-2.10 (m, 18H), 0.95 (d, J= 6.4 Hz, 6H)
Example 25
Synthesis of Ru complex 4ab
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 300 mg of green solid product 4ab was obtained (yield: 40%).
Ru complex (4ab) 1 HNMR (400 MHz, CDC1 3 ): δ 16.52 (s, Ru=CH), 7.58 (m, 1H), 7.09 (s, 4H), 6.93-6.60 (m, 6H ), 4.52 (m, 1H), 4.35 (s, 2H), 4.18 (s, 4H, NCH 2 CH 2 N), 3.89 (s, 6H), 2.49 (s, 12H), 2.40 (s, 6H).
Example 26
Synthesis of Ru complex 4ac
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 367 mg of green solid product 4ac was obtained (yield: 50%).
Ru complex (4ac) 1 HNMR (400 MHz, CDC1 3 ): δ 19.03 (s, Ru=CH), 8.38 (d, J = 2.0 Hz, 1H), 7.69 (d, J = 16.0 Hz, 1H), 7.44 (d, J = 7.6 Hz, 1H), 7.21-7.03 (m, 5H), 6.83-6.59 (m, 3H), 5.24 (t, J =12.0 Hz, 1H), 4.66 (d, J =12.0 Hz, 1H), 4.45 (m, 1H), 4.20-4.05 (m, 4H, NCH 2 CH 2 N), 3.62 (d, J =12.0 Hz, 1H), 2.69-2.03 (m, 18H), 1.18 (d, J= 5.6 Hz, 6H).
Example 27
Synthesis of Ru complex 4ad
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 374 mg of green solid product 4ad was obtained (yield: 49%). Ru complex (4ad) 1 HNMR (400 MHz, CDC1 3 ): δ 16.52 (s, Ru=CH), 7.59 (m, 1H), 7.09 (s, 4H), 6.92-6.84 (m, 4H ), 6.75-6.66 (m, 2H), 4.59 (m, 1H), 4.35 (s, 2H), 4.18 (s, 4H, NCH 2 CH 2 N), 3.89 (s, 3H), 2.49 (s, 12H), 2.40 (s, 6H, 18H), 0.93 (m, 6H).
Example 28
Synthesis of Ru complex 4ae
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 389 mg of green solid product 4ae was obtained (yield: 50%).
Ru complex (4ae) 1 HNMR (400 MHz, CDC1 3 ): δ 19.03 (s,lH, Ru=CH), 8.38 (d, J= 2.0 Hz, 1H), 7.69 (d, J= 16.0 Hz, 1H), 7.44 (d, J= 7.6 Hz, 1H), 7.21-7.03 (m, 5H), 6.83-6.59 (m, 3H), 5.24 (t, J =12.0 Hz, 1H), 4.66 (d, J =12.0 Hz, 1H), 4.45 (m, 1H), 4.20-4.05 (m, 4H, NCH 2 CH 2 N), 3.62 (d, J =12.0 Hz, 1H), 2.69-2.03 (m, 18H), 1.18 (d, J= 5.6 Hz, 6H).
Example 29
Synthesis of Ru complex 4af
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. I l l mg of green solid product 4af was obtained (yield: 15%).
Ru complex (4af) 1 HNMR (400 MHz, CDC1 3 ): δ 18.54 (s, lH, Ru=CH), 7.45 (d, J= 8.0 Hz, 1H), 7.24-7.19 (m, 4H), 7.06-6.96 (m, 6H), 6.14 (d, J= 13.2 Hz, 1H), 5.39 (d, J= 13.2 Hz, 1H), 4.07-3.77 (m, 7H), 3.52 (s, 3H), 2.65-2.30 (m, 18H).
Example 30
Synthesis of Ru complex 4ag
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 302 mg of green solid product 4ag was obtained (40% yield).
Ru complex (4ag) 1 HNMR (400 MHz, CDC1 3 ): δ 18.83 (s, lH, Ru=CH), 7.36-6.14 (m, 10H), 5.12 (t, J = 12.4 Hz, 1H), 4.50-3.42 (m, 12H), 2.62-2.05 (m, 18H). Example 31
Synthesis of Ru complex 4ah
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 376 mg of green solid product 4ah was obtained (yield: 51%).
Ru complex (4ah) 1 HNMR (400 MHz, CDC1 3 ): δ 18.90 (s, lH, Ru=CH), 7.60-6.36 (m, 10H), 5.25 (t, J = 12.0 Hz, 1H), 4.78 (d, J = 12.0 Hz, 1H), 4.05 (s, 4H, NCH 2 CH 2 N), 3.53 (s, 3H), 3.43 (d, J= 12.0 Hz, 1H), 2.56-2.13 (m, 21H).
Example 32
Synthesis of Ru complex 4aj
The synthetic procedure is the same as in Example 2 in 1.0 mmol scale. 390 mg of green solid product 4aj was obtained (yield: 55%).
Ru complex (4aj) 1 HNMR (400 MHz, CDC1 3 ): 519.45 (d, J = 9.6 Hz, Ru=CH), 8.18 (d, J = 7.6 Hz, 1H), 7.40-7.33 (m, 2H), 7.21-7.11 (m, 2H), 6.95-6.88 (m, 2H), 5.52 (m, 1H), 5.23 (m, 1H), 4.16-3.94 (m, 3H), 2.36-0.81 (m, 36H, PCy 3 ).
Example 33
Synthesis of Ru complex 4ak
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 299 mg of green solid product 4ak was obtained (yield: 37%).
Ru complex (4ak) 1 HNMR (400 MHz, CDC1 3 ): δ 19.08 (s, lH, Ru=CH), 7.97-6.33 (m, 10H), 5.08 (m, 2H), 4.34 (m, 1H), 4.02 (s, 4H, NCH 2 CH 2 N), 3.41 (m, 1H), 2.53-2.31 (m, 18H), 1.29 (s, 9H), 0.89-0.87 (m, 6H).
Example 34
Synthesis of Ru complex 4am
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 437 mg of green solid product 4am was obtained (yield: 54%).
Ru complex (4am) 1 HNMR (400 MHz, CDC1 3 ): δ 18.85 (s, lH, Ru=CH), 7.26-6.07 (m, 10H), 5.04 (t, J = 13.2 Hz, 1H), 4.48 (m, 1H), 4.39-4.33 (m, 2H), 4.15-4.02 (m, 4H, NCH 2 CH 2 N), 3.65 (m, 1H), 2.66-2.05 (m, 18H), 1.55 (m, 6H) , 1.38 (m, 6H). Example 35
Synthesis of Ru complex 4an
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 359 mg of green solid product 4an was obtained (yield: 46%).
Ru complex (4an) 1 HNMR (400 MHz, CDC1 3 ): δ 18.98 (s, lH, Ru=CH), 7.66-6.39 (m, 10H), 5.17 (t, J= 13.2 Hz, 1H), 4.71 (d, J= 13.2 Hz, 1H), 4.36 (m, 1H), 4.06 (brs, 4H, NCH 2 CH 2 N), 3.42 (d, J = 13.2 Hz, 1H), 2.63-2.09 (m, 21H), 1.09 (m, 6H).
Example 36
Synthesis of Ru complex 4ap
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 380 mg of green solid product 4ap was obtained (yield: 44%).
Ru complex (4ap) 1 HNMR (400 MHz, CDC1 3 ): δ 18.99 (s, lH, Ru=CH), 7.45-6.36 (m, 9H), 5.05 (m, 2H), 3.98-3.91 (m, 5H), 3.72 (d, J = 13.2 Hz, 1H), 2.48-2.34 (m, 19H), 1.45-0.95 (m, 21H).
Example 37
Synthesis of Ru complex 4aq
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 665 mg of green solid product 4aq was obtained (yield: 90%).
Ru complex (4aq) 1H- MR (400 MHz, CDC1 3 ): δ 18.75 (s, lH, Ru=CH), 7.50-7.44 (m, 2H), 7.04-6.36 (m, 9H), 5.32-5.21 (m, 1H), 4.65 (d, J = 13.2 Hz, 1H), 4.16-4.04 (m, 4H, NCH 2 CH 2 N), 3.59 (s, 3H), 3.48 (d, J= 13.2 Hz, 1H), 2.62-2.32 (m, 18H). Example 38
Synthesis of Ru complex 4ar
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 499 mg of green solid product 4ar was obtained (yield: 65%).
Ru complex (4ar) 1 HNMR (300 MHz, CDC13): δ 18.82 (s, lH, Ru=CH),
7.47-7.43 (m, 2H), 7.01-6.56 (m, 9H), 5.12-5.09 (m, 1H), 4.56-4.45 (m, 2H), 4.40-4.15 (m, 4H, NCH 2 CH 2 N), 3.48-3.45 (m, 1H), 2.64-2.04 (m, 18H), 1.10 (d, J = 6.4 Hz, 6H). Example 39
Synthesis of Ru complex 4as
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 467 mg of green solid product 4as was obtained (yield: 59%).
Ru complex (4as) 1 HNMR (400 MHz, CDC1 3 ): δ 18.82 (s, lH, Ru=CH), 8.15 (dd, J = 6.4, 1.2 Hz, 2H), 7.51 (d, J = 1.2 Hz, 1H), 7.44 (d, J = 1.2 Hz, 1H), 7.05-6.99 (m, 5H), 8.15 (d, J = 6.4Hz, 2H), 6.59-6.56 (m, 1H), 5.22 (m, 1H), 4.63 (m, 1H), 4.41(m, lH), 3.96 (m, 4H, NCH 2 CH 2 N), 3.55-3.52 (m, 1H), 2.66-2.33 (m, 18H), 1.14 (d, J= 6.4 Hz, 6H). Example 40
Synthesis of Ru complex 4at
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 341 mg of green solid product 4at was obtained (yield: 42%).
Ru complex (4at) 1 HNMR (400 MHz, CDC1 3 ): δ 19.02 (s, lH, Ru=CH), 7.87 (dd, J = 8.0, 1.2 Hz, 1H), 7.44 (dd, J = 7.2, 1.2 Hz, 1H), 7.25-7.03 (m, 9H), 5.37-5.30 (m, 1H), 4.76-4.74 (m, 1H), 4.16-4.01 (m, 4H, NCH 2 CH 2 N), 3.58-3.54 (m, 4H), 2.75 (s, 6H), 2.73-1.98 (m, 18H).
Example 41
Synthesis of Ru complex 4au The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 471 mg of green solid product 4au was obtained (yield: 51%).
Ru complex (4au) 1 HNMR (300 MHz, CDC13): δ 19.06 (s, lH, Ru=CH), 7.87 (d, J = 7.6Hz, 1H), 7.42 (d, J = 7.6Hz, 1H), 7.29 (d, J = 12.0 Hz, 1H), 7.11-6.56 (m, 8H), 5.22-5.19 (m, 1H), 4.63-4.64 (m, 1H), 4.45-4.42 (m, 1H), 4.14-4.01 (m, 4H, NCH 2 CH 2 N), 3.56-3.53 (m, 1H), 3.12-3.07 (m, 4H), 2.67-2.36 (m, 18H), 1.99-1.00 (m, 24H).
Example 42
Synthesis of Ru complex 4av
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 622 mg of green solid product 4av was obtained (yield: 74%).
Ru complex (4av) 1 HNMR (300 MHz, CDC13): δ 19.06 (s, lH, Ru=CH), 7.87 (d, J = 7.6Hz, 1H), 7.42 (d, J = 7.6Hz, 1H), 7.11-6.56 (m, 9H), 5.27-5.20 (m, 1H), 4.64-4.61 (m, 1H), 4.46-4.44 (m, 1H), 4.14-4.01 (m, 4H, NCH 2 CH 2 N), 3.59-3.56 (m, 1H), 3.12-3.07 (m, 4H), 2.75 (s, 6H), 2.67-2.36 (m, 18H), 1.13 (d, J= 6.0Hz, 6H).
Example 43
Synthesis of Ru complex 4aw
The synthetic procedure is the same as in Example 2 in 1.0 mmol scale. 626 mg of green solid product 4aw was obtained (yield: 77%).
Ru complex (4aw) 1 HNMR (400 MHz, CDC1 3 ): δ 19.56 (d, J = 9.6 Hz, Ru=CH),
8.21 (d, J = 8.0 Hz, 1H), 8.09 (d, J = 2.0 Hz, 1H), 8.10 (dd, J = 7.6, 2 Hz, 1H),
7.34-6.87 (m, 4H), 5.47-5.44 (m, 1H), 5.33-5.27 (m, 1H), 4.62-4.56 (m, 1H), 3.99-3.96 (m, 1H), 2.80 (s, 6H), 2.30-1.24 (m, 39H, PCy 3 ).
Example 44
Synthesis of Ru complex 4ax
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 421 mg of green solid product 4ax was obtained (yield: 47%). Ru complex (4ax) 1 HNMR (400 MHz, CDC1 3 ): δ 18.99 (s, lH, Ru=CH), 7.88 (dd, J = 8.0, 2.0 Hz, IH), 7.44 (dd, J = 7.2, 1.2 Hz, IH), 7.28-6.63 (m, 9H), 5.35-5.28 (m, IH), 4.75-4.72 (m, IH), 4.16-4.12 (m, 4H, NCH 2 CH 2 N), 3.61 (s, 3H), 3.56-3.52 (m, 4H), 3.10-3.06 (m, 4H), 2.63-2.05 (m, 18H), 1.37-0.98 (m, 14H).
Example 45
Synthesis of Ru complex 4ay
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 241 mg of green solid product 4ay was obtained (yield: 27%).
Ru complex (4ay) 1 HNMR (400 MHz, CDC1 3 ): δ 19.03 (s, IH, Ru=CH), 7.60 (d, J = 7.6 Hz, IH), 7.43 (d, J = 3.6 Hz, IH), 7.14 (s, IH), 7.09-7.00 (m, 5H), 6.81-6.57(m, 3H), 5.22 (m, IH), 4.64-4.61 (m, IH), 4.64-4.42 (m, 2H), 4.15-4.02 (m, 4H, NCH 2 CH 2 N), 3.16 (m, IH), 3.17 (m, IH), 2.67-2.00 (m, 18H), 1.85-1.00 (m, 16H).
Example 46
Synthesis of Ru complex 4ba
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 176 mg of green solid product 4ba was obtained (yield: 22%).
Ru complex (4ba) 1 HNMR (400 MHz, CDC1 3 ): δ 18.74 (s, IH, Ru=CH), 7.25-7.24 (m, IH), 7.19(s, IH), 7.14-7.04 (m, 7H), 6.93 (s, IH), 6.71 (s, IH), 6.41-6.40 (d, J=9.0 Hz, IH), 6.10-6.07 (d, J=12.0 Hz, IH), 4.52-4.49 (d, J=13.5Hz, IH), 4.33-4.29 (d, J=18.5 Hz, IH), 4.09 (s, 2H), 3.92 (s, 2H), 3.31 (s, 3H), 2.96-2.92 (d, J=19.0Hz, IH), 2.83 (s, 3H), 2.71(s, 3H), 2.47 (s, 3H), 2.39 (s, 3H), 2.06 (s, 3H), 2.02 (s, 3H).
Example 47
Synthesis of Ru complex 4bb
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 237 mg of green solid product 4bb was obtained (yield: 30%). Ru complex (4bb) 1 HNMR (400 MHz, CDC1 3 ): δ 18.74 (s, IH, Ru=CH), 7.27-7.25 (dd, J=8.0, 3.0 Hz, IH), 7.19 (s, IH), 7.14-7.05 (m, 7H), 6.93 (s, IH), 6.71 (s, IH), 6.42-6.40 (d, J=9.0 Hz, IH), 6.07-6.05 (d, J=12.5 Hz, IH), 4.65-4.61 (m, IH), 4.51-4.49 (d, J=12.5 Hz, IH), 4.24-4.20 (d, J=18.0 Hz, IH), 4.10 (s, 2H), 3.92 (s, 2H), 2.90-2.86 (d, J=18 Hz, IH), 2.83 (s, 3H), 2.71 (s, 3H), 2.47 (s, 3H), 2.39 (s, 3H), 2.07 (s, 3H), 2.03 (s, 3H), 0.90-0.82 (d, J=33.0, 6.5 Hz, 6H).
Example 48
Synthesis of Ru complex 4bc
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 578 mg of green solid product 4bc was obtained (yield: 73%).
Ru complex (4bc) 1 HNMR (400 MHz, CDC1 3 ): δ 18.72 (s, IH, Ru=CH),
7.24-7.22 (dd, J=8.5, 2.5 Hz, IH), 7.16 (s, IH), 7.07-7.04 (m, 4H), 6.91 (s, IH), 6.75
(s, IH), 6.66 (s, IH), 6.64(s, IH), 6.39-6.38 (d, J=8.0 Hz, IH), 6.02-6.00 (d, J=12.0 Hz, IH), 4.64-4.59 (m, IH), 4.50-4.47 (d, J=13.0 Hz, IH), 4.13-4.09 (d, J=18 Hz, IH),
4.08 (s, 2H), 3.90 (s, 2H), 3.83(s, 3H), 2.81 (s, 3H), 2.81-2.79 (d, J=11.5 Hz, IH),
2.69 (s, 3H), 2.45 (s, 3H), 2.39 (s, 3H), 2.08 (s, 3H), 2.01 (s, 3H), 0.89-0.81 (dd,
J=34.0, 6.0 Hz, 6H). Example 49
Synthesis of Ru complex 4bd
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 236 mg of green solid product 4bd was obtained (yield: 29%).
Ru complex (4bd) 1 HNMR (400 MHz, CDC1 3 ): δ 18.72 (s, IH, Ru=CH), 7.28-7.26 (m, IH), 7.19 (s, IH), 7.10-7.05 (m, 6H), 6.94 (s, IH), 6.82 (s, IH), 6.41-6.39 (d, J=9.5 Hz, IH), 6.07-6.04 (d, J=12.0 Hz, IH), 4.68-4.64 (m, IH), 4.45.4.43 (d, J=12.5 Hz, IH), 4.24-4.20 (d, J=18.0 Hz, IH), 4.09 (s, 2H), 3.93(s, 2H), 2.91-2.87 (d, J=18.5 Hz, IH), 2.81 (s, 3H), 2.70 (s, 3H), 2.47 (s, 6H), 2.10 (s, 3H), 2.03 (s, 3H), 0.93-0.87 (dd, J=24.0, 7.0 Hz, 6H). Example 50
Synthesis of Ru complex 4be
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 396 mg of green solid product 4be was obtained (yield: 49%).
Ru complex (4be) 1 HNMR (400 MHz, CDC1 3 ): δ 18.71 (s, 1H, Ru=CH),
7.29-7.25 (dd, J=8.5, 2.5 Hz, 1H), 7.19 (s, 1H), 7.13-7.06 (m, 4H), 6.94 (s, 1H), 6.82-6.77 (m, 3H), 6.42-6.39 (dd, J=9.5, 2.5 Hz, 1H), 6.08-6.05 (d, J=13.0 Hz, 1H), 4.66-4.64 (m, 1H), 4.47-4.45 (d, J=12.5 Hz, 1H), 4.21-4.18 (d, J=18 Hz, 1H), 4.10 (s, 2H), 3.93 (s, 2H), 3.89-3.86 (d, J=18 Hz, 1H), 2.83 (s, 3H), 2.70 (s, 3H), 2.48 (s, 3H), 2.42 (s, 3H), 2.11 (s, 3H), 2.02 (s, 3H), 0.92-0.85 (dd, J=26.5, 7.0 Hz, 3H).
Example 51
Synthesis of Ru complex 4bf
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 76 mg of green solid product 4bf was obtained (yield: 10%).
Ru complex (4bf) 1 HNMR (400 MHz, CDC1 3 ): δ 18.54 (s, 1H, Ru=CH), 7.16-6.87 (m, 7H), 6.15-6.13 (dd, J=10.0, 2.0 Hz, 1H), 5.44-5.41 (d, J=13.5 Hz, 1H), 4.76-4.71 (m, 1H), 4.37-4.34 (d, J=15.5 Hz, 1H), 3.96 (s, 4H, NCH 2 CH 2 N), 3.07-3.05 (d, J=13 Hz, 1H), 2.75-2.40 (m, 18H), 1.66 (s, 3H), 1.21-1.17 (dd, J=13.0, 6.5 Hz, 6H).
Example 52
Synthesis of Ru complex 6a
To a 50 mL two-necked round bottom flask, after filling with Ar atmosphere, were added ligand 5a (l .Ommol) and CuCl (3.0mmol, 3eq) and 30 mL dry DCM, followed by refilling with Ar three times and protected with Ar balloon in close system. Ru complex lb (l.Ommol) was added under Ar protection, and the mixture was stirred for 0.5 hr at room temperature.
After the reaction was complete, the solution was filtered and the filtrate was concentrated and slurred with silica gel. The crude was obtained by silica gel column chromatography and washed with methanol or pentane-DCM to obtain 453mg of yellow-green solid product 6a, yield: 79%.
Ru complex (6a) 1 HNMR (400 MHz, CDC1 3 ): δ 18.53 (s, 1H, Ru=CH), 8.59 (s, 1H), 7.28-6.49 (m, 11H), 4.160 (s, 4H, NCH 2 CH 2 N), 2.50 (s, 12H), 2.42 (s, 6H).
Example 53
Synthesis of Ru complex 6b
To a 50 mL two-necked round bottom flask, after filling with Ar atmosphere, were added ligand 5b (l .Ommol) and CuCl (3.0mmol, 3eq) and 30 mL dry DCM, followed by refilling with Ar three times and protected with Ar balloon in close system. Ru complex la (l .Ommol) was added under Ar protection, and the mixture was stirred for 0.5 hr at room temperature.
After the reaction was complete, the solution was filtered and the filtrate was concentrated and slurred with silica gel. The crude was obtained by silica gel column chromatography and washed with methanol or pentane-DCM to obtain 414mg yello-green solid product 6b, yield: 77%.
Ru complex (6b) 1 HNMR (400 MHz, CDC1 3 ): δ 19.20 (d, J = 10.8 Hz, Ru=CH), 8.82 (d, J = 9.2 Hz, 1H), 7.84 (m, 1H), 7.80 (d, J = 8.4 Hz, 1H), 7.45 (m, 4H), 2.46-1.29 (m, 33H, PCy 3 ).
Example 54
Synthesis of Ru complex 6c
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 664 mg of yellow-green solid product 6c was obtained (96% yield).
Ru complex (6c) 1 HNMR (400 MHz, CDC1 3 ): δ 18.52 (s, 1H, Ru=CH), 8.60(s,
1H), 7.28-7.13 (m, 7H), 7.02 (d, J = 8.8 Hz, 1H), 6.80 (m, 1H), 6.09 (d, J = 8.8 Hz, 1H), 4.16 (s, 4H, NCH 2 CH 2 N), 3.84 (s, 3H), 2.51 (m, 18H).
Example 55
Synthesis of Ru complex 6d The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 68 mg of yellow-green solid product 6d was obtained (31% yield).
Ru complex (6d): 1 HNMR (400 MHz, CDC1 3 ): δ 18.73 (s, 1H, Ru=CH), 8.62 (s, 1H), 7.67-7.46 (m, 3H), 7.11 (s, 4H), 6.78-6.65 (m, 5H), 4.13 (s, 4H, NCH 2 CH 2 N), 3.81 (s, 3H), 2.49 (m, 18H).
Example 56
Synthesis of Ru complex 6e
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 41 mg of yellow-green solid product 6e was obtained (24% yield).
Ru complex (6e) 1 HNMR (400 MHz, CDC1 3 ): δ 18.74 (s, 1H, Ru=CH), 8.60 (s, 1H), 7.69-7.49 (m, 3H), 7.12-7.04 (m, 8H), 6.80 (d, J = 8.7 Hz, 1H), 4.13 (s, 4H, NCH 2 CH 2 N), 2.50 (m, 18H). Example 57
Synthesis of Ru complex 6f
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 664 mg of yellow-green solid product 6f was obtained (17% yield).
Ru complex (6f) 1 HNMR (400 MHz, CDC1 3 ): δ 18.60 (s, 1H, Ru=CH), 8.58 (s, 1H), 7.48-7.29 (m, 2H), 7.02 (d, J = 8.8 Hz, 2H), 6.74-6.69 (m, 3H), 4.17 (s, 4H, NCH 2 CH 2 N), 3.85 (s, 3H), 2.52 (m, 18H).
Example 58
Synthesis of Ru complex 6g
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 35 mg of green solid product 6g was obtained (22% yield).
Ru complex (6g) 1H- MR (400 MHz, CDC1 3 ): δ 18.66 (s, 1H, Ru=CH), 8.56 (s, 1H), 7.50-7.34 (m, 2H), 7.26 (s, 4H), 7.00-6.40 (m, 5H), 4.14 (s, 4H, NCH 2 CH 2 N), 3.81 (s, 3H), 2.49 (m, 18H). Example 59
Synthesis of Ru complex 6h
The synthetic procedure is the same as in Example 52 in 1.0 mmol scale. 106 mg of yellow-green solid product 6h was obtained (37% yield).
Ru complex (6h) 1 HNMR (400 MHz, CDC1 3 ): δ 16.52 (s, 1H, Ru=CH), 8.43 (s,
1H, N=CH), 8.10 (s, 1H), 7.46-7.22 (m, 2H), 7.73-6.96 (m, 8H), 4.19 (s, 4H, NCH 2 CH 2 N), 3.95 (s, 3H), 3.87 (s, 3H), 2.49 (s, 12H), 2.48 (s, 6H).
Example 60
Synthesis of Ru complex 6j
To a 50 mL two-necked round bottom flask, after filling with Ar atmosphere, were added ligand 5j (l .Ommol) and CuCl (3.0mmol, 3eq) and 30 mL dry DCM, followed by refilling with Ar three times and protected with Ar balloon in close system. Ru complex la (l .Ommol) was added under Ar protection, and the mixture was stirred for 0.5 hr at room temperature.
After the reaction was complete, the solution was filtered and the filtrate was concentrated and slurred with silica gel. The crude was obtained by silica gel column chromatography and washed with methanol or pentane-DCM to obtain 190mg of red solid product 6j. The product is unstable. It is difficult to detect the structure by 1 HNMR. But the crude Ru complex 6j could be directly used for metathesis reaction.
Example 61
Synthesis of Ru complex 8a
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 208 mg of green solid product 8a was obtained, yield: 32%.
Ru complex (8a) 1 HNMR (400 MHz, CDC1 3 ): 516.80 (s, 1H, Ru=CH), 7.07 (s, 4H, aromatic H), 6.94 (m, 1H), 6.30 (d, J = 6.4 Hz, 1H), 4.11 (s, 4H, NCH 2 CH 2 N), 2.69 (s, 6H), 2.49 (s, (s, 12H), 2.42 (s, 6H).
Example 62 Synthesis of Ru complex 8b
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 59 mg of green solid product 8b was obtained (yield: 9%).
Ru complex (8b) 1 HNMR (400 MHz, CDC1 3 ): δ 16.97 (s, 1H, Ru=CH), 8.40 (dd, J = 8.8, 2.4 Hz, 1H), 7.65 (d, J = 2.4 Hz, 1H), 7.29 (d, J = 8.8 Hz, 1H), 7.07 (s, 4H), 4.20 (s, 4H, NCH 2 CH 2 N), 2.57 (s, 6H), 2.47 (s, 12H), 2.39 (s, 6H).
Example 63
Synthesis of Ru complex 8c
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 161 mg of green solid product 8c was obtained (24% yield).
Ru complex (8c) 1 HNMR (400 MHz, CDC1 3 ): δ 16.69 (s, 1H, Ru=CH), 8.36 (dd, J = 8.8, 2.4 Hz, 1H), 7.62 (d, J = 2.4 Hz, 1H), 7.18 (d, J = 8.8 Hz, 1H), 7.17-7.00 (m, 4H), 4.16-3.80 (m, 6H), 2.84-2.08 (m, 21H), 0.57 (t, J= 6.8 Hz, 3H).
Example 64
Synthesis of Ru complex 8d
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 103mg green solid product 8d was obtained, yield: 15%. The product is unstable, so it is difficult to detect the structure by 1 HNMR. But the crude Ru complex 6j could be directly used for metathesis reaction.
Example 65
Synthesis of Ru complex 8e
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 74mg green solid product 8d was obtained, yield: 15%. The product is unstable, so it is difficult to detect the structure by 1 HNMR. But the crude Ru complex 6j could be directly used for metathesis reaction. Example 66 Synthesis of Ru complex 8f
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 396 mg of green solid product 8f was obtained (yield: 59%).
Ru complex (8f) 1 HNMR (400 MHz, CDC1 3 ): 516.80 (s, 1H, Ru=CH), 8.18 (dd, J = 8.8, 2.4 Hz, 1H), 7.46 (d, J = 2.4 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H), 7.07 (s, 4H), 4.11 (s, 4H, NCH 2 CH 2 N), 3.91 (s, 3H), 2.58 (s, 6H), 2.47 (s, 12H), 2.43 (s, 6H).
Example 67
Synthesis of Ru complex 8g
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 530 mg of green solid product 8g was obtained (yield: 79%).
Ru complex (8g) 1 HNMR (400 MHz, CDC1 3 ): δ 16.70 (s, 1H, Ru=CH), 7.37 (m, 1H), 7.04-6.91 (m, 6H), 6.72 (d, J= 7.6 Hz, 1H), 5.05 (d, J = 11.6 Hz, 1H), 3.88-3.85 (m, 4H, NCH 2 CH 2 N), 3.52 (s, 3H), 3.44 (d, J= 11.6 Hz, 1H), 2.85-1.50 (m, 21H).
Example 68
Synthesis of Ru complex 8h
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 530 mg of green solid product 8h was obtained (yield: 74%).
Ru complex (8h) 1 HNMR (400 MHz, CDC1 3 ): δ 16.56 (s, 1H, Ru=CH), 8.33 (dd,
J= 8.4, 2.4 Hz, 1H), 7.56 (d, J= 2.4 Hz), 7.20-6.94 (m, 5H), 5.22 (d, J= 11.2 Hz, 1H), 4.21-3.96 (m, 4H, NCH 2 CH 2 N), 3.56 (s, 3H), 3.54 (d, J= 11.2 Hz, 1H), 2.94-0.92 (m, 21H). Example 69
Synthesis of Ru complex 8j
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 320 mg of green solid product 8j was obtained (yield: 43%).
Ru complex (8j) 1 HNMR (400 MHz, CDC1 3 ): δ 16.64 (s, 1H, Ru=CH), 8.34 (dd, J= 8.4, 2.4 Hz, 1H), 7.54 (d, J= 2.4 Hz, 1H), 7.25-6.93 (m, 5H), 5.17 (d, J= 11.2 Hz, 1H), 4.84-4.83 (m, 1H), 4.14-3.93 (m, 4H, NCH 2 CH 2 N), 3.45 (d, J = 11.2 Hz, 1H), 2.89-1.19 (m, 27 H).
Example 70
Synthesis of Ru complex 8k
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 530 mg of green solid product 8k was obtained (yield: 74%).
Ru complex (8k) 1 HNMR (400MHz, CDC1 3 ): δ 16.70 (s, 1H, Ru=CH), 7.18-7.13 (m, 3H), 7.05 (s, 1H), 6.96-6.94 (m, 2H), 6.48-6.45 (dd, J=8.0, 2.0 Hz, 1H), 5.19-5.16 (d, J=15.5 Hz, 1H), 4.17 (s, 2H), 3.94 (s, 2H), 3.62 (s, 3H), 3.50-3.47 (d, J=15.5 Hz, 1H), 2.94 (s, 3H), 2.80 (s, 3H), 2.49 (s, 3H), 2.32 (s, 6H), 2.00 (s, 6H).
Example 71
Synthesis of Ru complex 8m
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 430 mg of green solid product 8m was obtained (yield: 41%).
Ru complex (8m) 1 HNMR (400MHz, CDC1 3 ): δ 16.67 (s, 1H, Ru=CH),
7.10-7.16 (m, 3H), 7.02 (s, 1H), 6.91-6.94 (m, 2H), 6.43-6.45 (dd, J=8.75,2.5 Hz, 1H),
5.13-5.16 (d, J=15.5 Hz, 1H), 4.15 (s, 2H), 3.91(s, 2H), 3.59 (s, 3H), 3.44-3.47 (d, J=15.0 Hz, 1H), 2.92 (s, 3H), 2.77(s, 3H), 2.47 (s, 3H), 2.29 (s, 6H), 1.97 (s, 6H)..
Example 72
Synthesis of Ru complex 8n
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 599 mg of green solid product 8n was obtained (yield: 87%).
Ru complex (8n) 1 HNMR (400 MHz, CDC1 3 ): 516.82 (s, 1H, Ru=CH), 7.12-7.02 (m, 5H), 6.64 (m, 1H), 6.51-6.48 (m, 1H), 4.15 (s, 4H, NCH 2 CH 2 N), 3.95-3.92 (m, 1H), 3.74 (s, 3H), 2.50-2.37 (m, 18H), 0.96 (d, J= 6.4 Hz, 1H). Example 73
Synthesis of Ru complex 8p
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 379 mg of green solid product 8p was obtained (yield: 48%).
Ru complex (8p) 1 HNMR (400 MHz, CDC1 3 ): 517.58 (d, J = 6.0 Hz, 1H,
Ru=CH), 7.59-7.55 (m, 2H), 7.48 (d, J = 8.4 Hz, 1H), 7.22 (dd, J = 2.4, 8.8 Hz, 1H), 7.14 (d, J= 8.4 Hz, 1H), 6.78 (d, J= 8.8 Hz, 1H), 4.80 (d, J= 12.8 Hz, 1H), 4.50-4.47 (m, 1H), 4.05 (d, J= 12.8 Hz, 1H), 2.704 (s, 3H), 2.38-0.78 (m, 39H, PCy 3 ). Example 74
Synthesis of Ru complex 8q
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 602 mg of green solid product 8q was obtained (yield: 77%).
Ru complex (8q) 1 HNMR (400 MHz, CDC1 3 ): 516.87 (s, 1H, Ru=CH), 7.41 (dd, 7 = 2, 8.4 Hz, 1H), 7.19-7.13 (m, 5H), 7.031 (d, 7 = 8.4 Hz, 1H), 6.93 (d, 7 = 7.2 Hz, 1H), 6.77-6.76 (m, 2H), 6.65 (t, 7 = 7.2 Hz, 1H), 4.66 (d, 7 = 12.4 Hz, 1H), 4.48-4.43 (m, 1H), 4.02-3.98 (m, 5H), 2.54-2.30 (m, 18H), 2.25 (s, 3H), 1.29 (d, 7= 6 Hz, 6H).
Example 75
Synthesis of Ru complex 8r
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 302 mg of green solid product 8r was obtained (yield: 37%).
Ru complex (8r) 1 HNMR (400 MHz, CDC1 3 ): 516.84 (s, 1H, Ru=CH), 7.18 (d, 7 = 8.4 Hz, 1H), 7.81 (m, 5H), 6.75 (m, 1H), 6.62 (d, 7 = 8.8 Hz, 1H), 6.32 (d, 7 = 8.4 Hz, 1H), 4.29-4.24 (m, 1H), 4.11 (s, 4H, NCH 2 CH 2 N), 3.85 (d, 7= 14.0 Hz, 1H), 3.09 (d, 7= 14.0 Hz, 1H), 2.74 (s, 3H), 2.43-2.28 (m, 18H), 1.10 (d, 7= 6.0 Hz, 6H).
Example 76
Synthesis of Ru complex 10a
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 128 mg of green solid product 10a was obtained (yield: 19%). The product is unstable, so it is difficult to detect the structure by 1 HNMR. But the crude Ru complex 10a could be directly used for metathesis reaction. Example 77
Synthesis of Ru complex 10b
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 97 mg of green solid product 10b was obtained (yield: 15%). The product is unstable, so it is difficult to detect the structure by 1 HNMR. But the crude Ru complex 10b could be directly used for metathesis reaction.
Example 78
Synthesis of Ru complex 10c
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 29 mg of green solid product 10c was obtained (yield: 5%).
Ru complex (10c) 1 HNMR (400 MHz, CDC1 3 ): δ 18.68 (s, 1H, Ru=CH), 8.44 (dd, J = 8.4, 2.4 Hz, 1H), 8.20 (d, J = 8.4 Hz, 1H), 7.60 (d, J = 2.4 Hz, 1H), 7.13 (s, 4H), 4.14 (s, 4H, NCH 2 CH 2 N), 3.97 (s, 3H), 2.48 (s, 12H), 2.459 (s, 6H). Example 79
Synthesis of Ru complex lOd
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 238 mg of green solid product lOd was obtained (yield: 34%).
Ru complex (lOd) 1 HNMR (400 MHz, CDC1 3 ): δ 18.71 (s, 1H, Ru=CH), 8.42 (dd, J = 9.0, 2.4 Hz, 1H), 8.18 (d, J = 9.0 Hz, 1H), 7.60 (d, J = 2.4 Hz, 1H), 7.13 (s, 4H), 5.25 (m, 1H), 4.13 (s, 4H, NCH 2 CH 2 N), 2.46 (m, 18H), 1.24 (d, J= 6.0 Hz, 6H,).
Example 80
Synthesis of Ru complex lOe
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 235 mg of green solid product lOe was obtained (yield: 34%).
Ru complex (lOe) 1 HNMR (400 MHz, CDC1 3 ): δ 18.56 (s, 1H, Ru=CH), 7.98 (d, J =8.8 Hz, 1H), 8.18 (dd, J = 8.8, 2.4 Hz, 1H), 7.11 (s, 4H), 7.06 (d, J = 2.4 Hz, 1H), 5.23 (m, 1H), 4.11 (s, 4H, NCH 2 CH 2 N), 2.45 (m, 18H), 1.28 (d, J= 6.0 Hz, 6H).
Example 81
Synthesis of Ru complex lOf
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 274 mg of green solid product lOf was obtained (yield: 37%).
Ru complex (lOf) 1 HNMR (400 MHz, CDC1 3 ): 1H- MR (400 MHz, CDC1 3 ): δ
18.74 (s, 1H, Ru=CH), 8.21 (dd, J= 8.0, 2.4 Hz, 1H), 8.08 (d, J= 8.0 Hz, 1H), 7.54 (d, J = 2.4 Hz, 1H), 7.12 (s, 4H), 5.32 (m, 1H), 5.25 (m, 1H), 4.13 (s, 4H, NCH 2 CH 2 N), 2.47 (m, 18H), 1.43 (d, J= 6.0 Hz), 1.24 (d, J= 6.0 Hz, 6H). Example 82
Synthesis of Ru complex lOg
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 440 mg of green solid product lOg was obtained (yield: 53%).
Ru complex (lOg) 1 HNMR (400 MHz, CDC1 3 ): δ 18.60 (s, 1H, Ru=CH), 8.01 (d, J =8.4 Hz, 1H), 7.59 (dd, J = 1.6, 8.4 Hz, 1H), 7.31-7.23 (m, 1H), 7.24 (dd, J = 2.8, 8.8 Hz, 1H), 6.81 (d, J =8.8 Hz, 1H), 6.71 (d, J = 2.0 Hz, 1H), 5.33 (s, 2H), 4.52 (m, 1H), 4.16 (s, 4H, NCH 2 CH 2 N), 2.51 (s, 12H), 2.48 (s, 6H), 1.28 (d, 6H, J= 6.0 Hz).
Example 83
Synthesis of Ru complex lOh
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 183 mg of green solid product lOg was obtained (yield: 23%).
Ru complex (lOg) 1 HNMR (400 MHz, CDC1 3 ): δ 18.60 (s, 1H, Ru=CH), 8.00 (d, J =8.8 Hz, 1H), 7.55 (d, J = 8.4 Hz, 1H), 7.32-7.29 (m, 1H), 7.14 (s, 4H), 7.01-6.70 (m, 4H), 5.38 (s, 2H), 4.56 (m, 1H), 4.16 (s, 4H, NCH 2 CH 2 N), 2.71 (s, 12H), 2.52 (s, 6H), 1.32 (d, 7= 6.0 Hz, 6H).
Example 84
Synthesis of Ru complex lOj
The synthetic procedure is the same as in Example 1 in 1.0 mmol scale. 345 mg of yellow solid product lOj was obtained (yield: 41%).
It is confirmed byRu complex (lOj) 1 HNMR (400 MHz, CDC1 3 ): δ 18.75 (s, IH, Ru=CH), 8.45 (dd, 7 =8.8, 1.6 Hz, IH), 8.21 (d, 7 =8.8 Hz, IH), 7.64 (d, 7 =1.6 Hz, IH), 7.39-7.25 (m, 2H), 7.17 (s, 4H), 6.83 (d, 7 =8.8 Hz, IH), 5.37 (s, 2H), 4.53 (m, IH), 4.15 (s, 4H, NCH 2 CH 2 N), 2.51 (m, 18H), 1.40 (d, 7= 6.0 Hz, 6H).
Example 85
Synthesis of Ru complex 11a
The Ru complex (Grela catalyst 2f, l .Ommol) and 4-chlorin pyridine ligand (lOmmol) were reacted directly to form another Ru complex 11a in 20 mL of anhydrous DCM in a 100 mL of three-neck flask filled with inert gas (Ar), and the reaction mixture was stirred for 0.5 hr at room temperature. After complete, 20mL of pentane (-10 ° C) was added into reaction solution, then filtered and washed with MeOH to obtain 747 mg of yellow-green solid product 11a, yield: 95%.
Ru complex (11a) 1 HNMR (400 MHz, CDC1 3 ): δ 17.00 (s, IH), 8.47-6.83 (m,
11H), 4.91 (m, IH), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, 7= 4.4 Hz, 6H).
Example 86
Synthesis of Ru complex lib
The synthetic procedure is the same as in Example 85. 394 mg of yellow-green solid product lib was obtained (yield: 48%).
Ru complex (lib) 1 HNMR (400 MHz, CDC1 3 ): δ 16.49 (s, IH), 8.90-8.50 (m,
2H), 7.86 (d, 7 = 7.2 Hz, IH), 7.47 (dd, 7 = 2.0, 7.2Hz, IH), 7.33 (m, IH), 7.27 (m,
IH), 7.08 (s, 3H), 6.90 (d, 7 = 1.6 Hz, IH), 6.74-6.72 (m, IH), 4.87-4.84 (m, IH), 4.19 (s, 4H), 2.48-2.42 (m, 18H), 1.27 (d, 7= 4.0 Hz, 6H). Example 87
Synthesis of Ru complex 11c
The synthetic procedure is the same as in Example 85. 733 mg of yellow-green solid product 11c was obtained (yield: 95%).
Ru complex (11c) 1 HNMR (400 MHz, CDC1 3 ): δ 16.56 (s, 1H), 7.47 (dd, J = 2.0, 7.2 Hz, 1H), 7.31-7.27 (m, 5H), 7.20-7.19 (m, 3H), 7.08-6.94 (m, 1H),6.72 (d, J = 6.4Hz, 1H), 4.85-4.81 (m, 1H), 4.18 (s, 3H), 3.85 (s, 4H), 2.48-2.31 (m, 18H), 1.26 (d, J= 6.0 Hz, 6H).
Example 88
Synthesis of Ru complex lid
The synthetic procedure is the same as in Example 85. 403 mg of yellow-green solid product lid was obtained (yield: 52%).
Ru complex (lid) 1 HNMR (400 MHz, CDC1 3 ): δ 16.49 (s, 1H), 8.67 (m, 2H), 7.47 (d, J= 5.6 Hz, 1H), 7.37 (m, 3H), 7.08 (s, 3H),6.73 (d, J= 6.8Hz, 1H), 4.85-4.83 (m, 1H), 4.19 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J= 4.4 Hz, 6H).
Example 89
Synthesis of Ru complex lie
The synthetic procedure is the same as in Example 85. 458 mg of yellow-green solid product lie was obtained (yield: 59%).
It is confirmed by Ru complex (lie) 1 HNMR (400 MHz, CDC1 3 ): δ 16.52 (s, 1H), 8.60-8.51 (m, 2H), 7.67 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 2.4 Hz, 1H), 7.06 (s, 4H), 6.88 (d, J = 2.4 Hz, 1H), 6.71 (d, J = 8.0 Hz, 2H), 4.84-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 18H), 1.24 (d, J= 4.0 Hz, 6H).
Example 90
Synthesis of Ru complex llf
The synthetic procedure is the same as in Example 85. 733 mg of yellow-green solid product llf was obtained (yield: 97%).
Ru complex (llf) 1 HNMR (400 MHz, CDC1 3 ): δ 16.57 (s, 1H), 7.63-6.69 (m, 11H), 4.83-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 21H), 1.24 (d, J= 4.0 Hz, 6H). Example 91
Synthesis of Ru complex llg
The synthetic procedure is the same as in Example 85. 330 mg of yellow-green solid product llg was obtained (yield: 37%).
Ru complex (llg) 1 HNMR (400 MHz, CDC1 3 ): δ 18.67 (s, 1H), 8.40 (m, 1H), 7.47-6.91 (m, 13H), 6.58 (m, 1H), 4.12 (m, 6H), 2.63-2.27 (m, 19H), 1.00 (d, J = 4.0 Hz, 6H).
Example 92
Synthesis of Ru complex llh
The synthetic procedure is the same as in Example 85. 619 mg of yellow-green solid product llh was obtained (yield: 73%).
Ru complex (llh) ! HNMR (400 MHz, CDC1 3 ): δ 18.67 (s, 1H), 8.43 (s, 1H), 7.45-7.35 (m, 3H), 7.19-6.93 (m, 10H), 6.60 (d, J = 7.6 Hz, 1H), 4.15 (m, 6H), 2.52-2.28 (m, 19H), 1.08-0.89 (m, 6H).
Example 93
Synthesis of Ru complex llj
The synthetic procedure is the same as in Example 85. 416 mg of yellow-green solid product llj was obtained (yield: 49%).
Ru complex (llj) 'HNMR (400 MHz, CDC1 3 ): δ 18.67 (s, 1H), 8.40 (m, 1H), 7.69-6.90 (m, 13H), 6.60 (m, 1H), 4.12 (m, 6H), 2.62-2.17 (m, 19H), 1.00 (d, J = 4.0 Hz, 6H).
Example 94
Synthesis of Ru complex Ilk The synthetic procedure is the same as in Example 85. 561 mg of yellow-green solid product Ilk was obtained (yield: 63%).
Ru complex (Ilk) 1 HNMR (400 MHz, CDC1 3 ): 518.69 (s, 1H), 8.42 (s, 2H), 7.62-6.93 (m, 16H), 6.60 (dd, J = 2.0, 7.6 Hz, 2H), 4.14 (s, 6H), 2.52-2.27 (m, 18H), 0.98 (d, J= 4.4 Hz, 6H).
Example 95
Synthesis of Ru complex 11m
The synthetic procedure is the same as in Example 85. 685 mg of yellow-green solid product 11m was obtained (yield: 78%).
Ru complex (11m): 1H- MR (400 MHz, CDC1 3 ): δ 16.85 (s, 1H), 8.42-7.07 (m, 15H), 4.95 (m, 1H), 4.19 (s, 4H), 2.45-2.29 (m, 18H), 1.29 (d, J= 4.4 Hz, 6H).
Example 96
Synthesis of Ru complex lln
The synthetic procedure is the same as in Example 85. 704 mg of yellow-green solid product lln was obtained (yield: 85%).
Ru complex (lln) 1 HNMR (400 MHz, CDC1 3 ): 516.85 (s, 1H), 8.47-6.85 (m, 16H), 4.94 (m, 1H), 4.19 (s, 4H), 2.40-2.29 (m, 18H), 1.29 (d, J= 4.4 Hz, 6H).
Example 97
Synthesis of Ru complex lip
The synthetic procedure is the same as in Example 85. 797 mg of yellow-green solid product lip was obtained (yield: 96%).
Ru complex (lip) 1 HNMR (400 MHz, CDC1 3 ): 517.00 (s, 1H), 8.47-6.82 (m, 11H), 4.90 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J= 4.4 Hz, 6H).
Example 98
Synthesis of Ru complex llq
The synthetic procedure is the same as in Example 85. 365 mg of yellow-green solid product llq was obtained (yield: 47%).
Ru complex (llq) 1 HNMR (400 MHz, CDC1 3 ): δ 17.33 (s, 1H), 8.71 (s, 1H),
8.56 (d, J = 3.2 Hz, 1H), 7.84 (d, J = 6.0Hz, 1H), 7.41-7.34 (m, 1H), 7.23-7.21 (m,
1H), 7.01 (dd, J= 3.2, 9.6 Hz), 5.23-5.21 (m, 1H), 2.37-0.90 (m, 33H).
Example 99
Synthesis of Ru complex 11 r
The synthetic procedure is the same as in Example 85. 604 mg of yellow-green solid product llr was obtained (yield: 69%).
Ru complex (llr) 1 HNMR (400 MHz, CDC1 3 ): δ 18.65 (s, 1H), 8.56 (s, 1H),
7.50-6.39 (m, 20H), 4.14 (s, 4H), 3.80 (s, 3H), 2.42-2.29 (m, 18H).
Example 100
Synthesis of Ru complex 4i
Starting material 4-SM (44g, lOOmmol) and anhydrous ethanol (250mL) were added into a 500 mL three-necked flask filled with inert gas (Ar), followed by adding NaOEt (400mmol, 4.0eq) was quickly added with agitation. The reaction mixture was heated to 60 ° C . After the reaction was completed in 0.5-1.0 hr, 120 mL of water was added into flask, and the aqueous layer was extracted with pentane (200 mL><3), and the combined organic layers were washed with brine (150 mL><2) solution, then dried over NaS0 4 and concentrated to obtain about 50 mL of crude carbine intermediate 4-1 directly for next step at 0-5 ° C .
RuCl 2 (PPh 3 ) 3 (29g, 30mmol) was dissolved in 250 mL of anhydrous DCM in a 500 mL three-neck flask filled with inert gas (Ar), and the DCM solution was cooled to -70 ° C, then the previously prepared crude carbine intermediate 4-1 (50 mL) was added into the DCM solution at -70 ° C . After 10 min, the solution was heated to room temperature, and CuCl (lOOmmol) was added. After completed in 30 min, the reaction solution was filtered and purified by silica gel column chromatography (eluting solution: n-hexane:DCM = 2: 1 to pure DCM). The product was concentrated and washed by anhydrous n-hexane. After dried by vacuum, the Ru complex intermediate 4-2 (19.3g) was obtained.
The intermediate 4-2 (lO.Ommol) and tricyclohexylphosphine (PCy 3 , 20mmol, 2.0eq.) were dissolved in DCM (30mL) in a 250 mL three-neck flask filled with inert gas (Ar), then stirred at 20 ° C for about 30 min. After completed, the crude product was purified by flash column to obtain dark-green solid. The solid product was washed with anhydrous methanol and n-hexane to obtain green solid product 4i (crude yield: 60-70%). The product 4i is not stable and difficult to analyze the structure by 1 HNMR. But the crud Ru complex 4i can be used directly to prepare 4j in next step.
Example 101
Synthesis of Ru complex 4j
The Ru complex 4i (5.0mmol) and a ligand H 2 IMes(H)(CCl 3 ) (4-4, lO.Ommol, 2.0eq.) were dissolved in anhydrous toluene (30mL) in a 100 mL two-necked flask filled with Ar gas. The reaction mixture was heated to 80 ° C for 1.5hr. After the reaction was completed, the solution was cooled and filtered, then purified by flash column to obtain dark-green product. The crude product was washed by methanol and pentane-DCM to offer 2.3g of stable green solid product 4j (yield: 59%).
Ru complex 4j is confirmed by 1 HNMR (400 MHz, CDC1 3 ): δ 18.88 (s, lH, Ru=CH), 7.57-6.44 (m, 11H, aromatic H), 5.36 (t, J= 13.2 Hz, 1H, H), 4.16-4.02 (m, 5H, NCH 2 , NCH 2 CH 2 N), 4.01 (d, J = 13.2 Hz, 1H, NCH 2 ), 2.75-2.00 (m, 19H, CH(CH 3 ) 2 , aromatic CH 3 ), 1.01-0.90 (m, 6H, CH(CH3) 2 ).
Example 102
Synthesis of Ru complex llh
The Ru complex 4j (0.2mmol) and 4-chlorin pyridine 4-chlorin pyridine ligand (4-5, 2.0mmol) were reacted directly to form another Ru complex llh in 10 mL of anhydrous DCM in a 100 mL three-neck flask filled with inert gas (Ar). Preparation method and result of the Ru complex llh was the same as described in Example 92. 619 mg of yellow-green solid product llh was obtained (yield: 73%).
Ru complex llh is confirmed by 1 HNMR (400 MHz, CDC1 3 ): δ 18.67 (s, 1H), 8.43 (s, 1H), 7.45-7.35 (m, 3H), 7.19-6.93 (m, 10H), 6.60 (d, J= 7.6 Hz, 1H), 4.15 (m, 6H), 2.52-2.28 (m, 19H), 1.08-0.89 (m, 6H).
Example 103
Synthesis of Ru complex 6h
The Ru complex (Zhan catalyst 2b, l.Ommol) and a new ligand 5h (1.5mmol) were dissolved in 20 mL of anhydrous DCM and reacted directly to form the desired Ru complex 6h in the preaence of CuCl (3.0mmol) in a 100 mL of three-neck flask filled with inert gas (Ar). The reaction mixture was stirred for 0.5 hr at room temperature. After complete, the reaction solution was filtered and purified by flask column. 378mg of yellow-green solid product 6h was obtained, yield: 52%.
Ru complex 6h is confirmed by 1 HNMR (400 MHz, CDC1 3 ): δ 16.52 (s, 1H, Ru=CH), 8.43 (s, 1H, N=CH), 8.10 (s, 1H), 7.46-7.22 (m, 2H), 7.73-6.96 (m, 8H), 4.19 (s, 4H, NCH 2 CH 2 N), 3.95 (s, 3H), 3.87 (s, 3H), 2.49 (s, 12H), 2.48 (s, 6H).
Example 104
RCM reaction
RCM test by selecting the Ru Complexes of Examples 1-103 as Catalyst
General Procedure for RCM Catalyzed by Ru Complex in DCM: Olefin substrate (15 or 17, 50mg/each, respectivrly) was dissolved in 1.0 mL of freshly distilled DCM in a 15mL two-neck round-bottom flask under Ar at 20-25 °C, then Ru catalyst (2 mol% of Ru complex selected from Examples 1-103, respectively) was added into the DCM solution. The kinetic data for conversion of RCM reactions in Equations 1-2 were determined by HPLC at 10 min., 30 min. 1.5 hr, 3.0 hr and until completed overnight. The RCM product (16 and 18, respectivrly) was determined and the conversion results of RCM reactions were listed in Tables 1-1, 1-2, 1-3, 1-4, 1-5, and 2 above, respectively.
The RCM product 16 is confirmed by 1 HNMR (400 MHz, CDC1 3 ): δ 7.72 (d, J = 8.2 Hz„ 1H), 7.32 (d, J = 8.0 Hz, 1H), 5.66 (d, J = 4.4 Hz, 1H), 4.11 (d, J = 4.4 Hz, 1H), 2.42 (s, 3H). in z calculated: 222.1; found: 222.2. The RCM product 18 is confirmed by 1HNMR (400 MHz, CDC1 3 ): δ 7.78 (d, 2H, J = 8.21Hz), 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (s, 3H). (M+H + ) : m/z calculated : 300.1 , found : 300.2. Example 105
Catalyst Screening for Cross Metathesis Reaction
CM test by selecting the Ru Complexes of Examples 1-103 as Catalyst
General Procedure for CM Catalyzed by Ru Complex in DCM: Olefin substrate (19, 200mg/each, respectivrly) was dissolved in 3.0 mL of freshly distilled DCM in a 15mL two-neck round-bottom flask under Ar at 20-25 °C, then Ru catalyst (0.1 mol% of Ru complex selected from Examples 1-103, respectively) was added into the DCM solution. The CM reaction results are described in section of Equation 3 above.
Example 106
Catalyst Screening for ROMP reaction without solvent
ROMP test by selecting the Ru Complexes of Examples 1-103 as Catalyst
General Procedure for ROMP Catalyzed by Ru Complex without solvent for some liquid olefin substrates: Olefin substrate (21, 23 or 25, 5mL/each, respectivrly) was added into a 25mL flat-bottom bottle under Ar at 40-50°C, then Ru catalyst (0.1 mol% of Ru complex selected from Examples 1-103, respectively) was added with agitation. The kinetic data and ROMP results for products 22, 24 and 26 are described in each section of Equation 4-6 above, respectively.
Example 107
Catalyst Screening for ROMP reaction with solvent
ROMP test by selecting the Ru Complexes of Examples 1-103 as Catalyst
General Procedure for ROMP Catalyzed by Ru Complex in solution: 0.5g of cyclo-olefin substrate (21, 23, 25, 27, 29, or 31, respectivrly) was dissolved in 10 mL of freshly distilled DCM in a 25mL two-neck round-bottom flask under Ar at 20-25 °C, then Ru catalyst (0.1 mol% of Ru complex selected from Examples 1-103, respectively) was added into the DCM solution. The ROMP results for products 22, 24, 26 , 28, 30 and 32 are described in each section of Equation 4-9 above, respectively.
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