Claims
- 1. A ligand represented by the formula or its enantiomer:
- 2. The ligand of claim 1, wherein said substituted alkyl has one or more substituents, each independently selected from the group consisting of: halogen, ester, ketone, carboxylic acid, hydroxy, alkoxy, aryloxy, thiol, alkylthio and dialkylamino.
- 3. The ligand of claim 1, wherein said alkylene is selected from the group consisting of compounds represented by the formula: —(CH2)n—, wherein n is an integer in the range of from 1 to 8.
- 4. The ligand of claim 1, wherein each of said aryl groups optionally has one or more substituents, each independently selected from the group consisting of: halogen, ester, ketone, sulfonate, phosphonate, hydroxy, alkoxy, aryloxy, thiol, alkylthiol, nitro, amino, vinyl, substituted vinyl, carboxylic acid, sulfonic acid and phosphine.
- 5. The ligand of claim 1, wherein each of said arylene groups optionally has one or more substituents, each independently selected from the group consisting of: halogen, ester, ketone, sulfonate, phosphonate, hydroxy, alkoxy, aryloxy, thiol, alkylthiol, nitro, amino, vinyl, substituted vinyl, carboxylic acid, sulfonic acid and phosphine.
- 6. The ligand of claim 1, wherein each of said arylene groups is independently selected from the group consisting of: 1,2-divalent phenyl, 2,2′-divalent-1,1′-biphenyl, 2,2′-divalent-1,1′-binaphthyl and ferrocene.
- 7. The ligand of claim 1, wherein said ligand is a racemic mixture of enantiomers.
- 8. The ligand of claim 1, wherein said ligand is a non-racemic mixture of enantiomers.
- 9. The ligand of claim 1, wherein said ligand is one of the enantiomers.
- 10. The ligand of claim 1, having an optical purity of at least 85% ee.
- 12. The ligand of claim 1, having an optical purity of at least 95% ee.
- 13. The ligand of claim 1, wherein said ligand is selected from the group consisting of compounds represented by the following formulas:
- 14. The ligand of claim 1, wherein said ligand is selected from the group consisting of compounds represented by the following formulas:
- 15. The ligand of claim 1, wherein said ligand is selected from the group consisting of compounds represented by the formulas:
- 16. The ligand of claim 1, represented by the formula:
- 17. The ligand of claim 1, represented by the formula:
- 18. The ligand of claim 1, represented by the formula:
- 19. A catalyst prepared by a process comprising:
contacting a transition metal salt, or a complex thereof, and a ligand selected from the group consisting of compounds represented by the formula or its enantiomer: 215wherein each X and X is independently selected from the group consisting of: alkyl, aryl, substituted alkyl, substituted aryl, OR, SR. NR2, COOR, halide, SiR3, P(O)R2, P(O)(OR)2 and P(OR)2; wherein each Z and Z1 is independently selected from the group consisting of: alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR, halide, SiR3, P(O)R2, P(O)(OR)2 and P(OR)2; or wherein Z and Z1 together form the bridging group A-B-A1; wherein each Z′, Z″, Z1′ and Z1″ is independently selected from the group consisting of: H, alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR, halide, SiR3, P(O)R2, P(O)(OR)2 and P(OR)2; or wherein Z′ and Z together form the bridging group A′-B-A; Z′ and Z together form a fused cycloaliphatic or aromatic group; Z1 and Z1′ together form the bridging group A1-B1-A1′; and/or Z1 and Z1′ together form a fused cycloaliphatic or aromatic group; wherein each A, A′, A1 and A1′ is independently selected from the group consisting of: O, CH2, NH, NR, S, CO and a bond; wherein each B and B1 is independently selected from the group consisting of: linear, branched or cyclic alkylene of 1 to 6 carbon atoms, arylene of 6 to 12 carbon atoms. O, CH2, NH, NR, S, CO, SO2, P(O)R, P(O)OR, POR, SiR2 and a bond; wherein each T is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, substituted aryl, alkoxide, aryloxide, R, R′, R″, YR′, YR″, Y′R′ and Y″R″; or wherein two T groups together form an alkylene, arylene, alkylenediamino, arylenediamino, alkelenedioxyl or arylenedioxyl; wherein each T′ is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, substituted aryl, alkoxide, aryloxide, R, R′, R″, YR′, YR″, Y′R′ and Y″R″; or wherein two T′ groups together form an alkylene, arylene, alkylenediamino, arylenediamino, alkelenedioxyl or arylenedioxyl; wherein each R, R′ and R″ is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, aralkyl and alkaryl of 1 to 22 carbon atoms; or wherein two R groups, two R′ groups or two R″ group together form an alkylene or arelene group; and wherein each Y, Y′ and Y″ is independently selected from the group consisting of: O, CH2, NH, S and a bond between carbon and phosphorus; with the proviso that when the Y group at the 2′ position is a bond between carbon and phosphorus, X′ is hydrogen.
- 20. The catalyst of claim 19, wherein said substituted alkyl has one or more substituents, each independently selected from the group consisting of: halogen, ester, ketone, carboxylic acid, hydroxy, alkoxy, aryloxy, thiol, alkylthio and dialkylamino.
- 21. The catalyst of claim 19, wherein said alkylene is selected from the group consisting of compounds represented by the formula: —(CH2)n—, where n is an integer in the range of from 1 to 8.
- 22. The catalyst of claim 19, wherein each of said aryl groups optionally has one or more substituents, each independently selected from the group consisting of: halogen, ester, ketone, sulfonate, phosphonate, hydroxy, alkoxy, aryloxy, thiol, alkylthiol, nitro, amino, vinyl, substituted vinyl, carboxylic acid, sulfonic acid and phosphine.
- 23. The catalyst of claim 19, wherein each of said arylene groups optionally has one or more substituents, each independently selected from the group consisting of: halogen, ester, ketone, sulfonate, phosphonate, hydroxy, alkoxy, aryloxy, thiol, alkylthiol, nitro, amino, vinyl, substituted vinyl, carboxylic acid, sulfonic acid and phosphine.
- 24. The catalyst of claim 19, wherein each of said arylene groups is independently selected from the group consisting of: 1,2-divalent phenyl, 2,2′-divalent-1,1′-biphenyl, 2,2′-divalent-1,1′-binaphthyl and ferrocene.
- 25. The catalyst of claim 19, wherein said ligand is a racemic mixture of enantiomers.
- 26. The catalyst of claim 19, wherein said ligand is a non-racemic mixture of enantiomers.
- 27. The catalyst of claim 19, wherein said ligand is one of the enantiomers.
- 28. The catalyst of claim 19, having an optical purity of at least 85% ee.
- 29. The catalyst of claim 19, having an optical purity of at least 95% ee.
- 30. The catalyst of claim 19, wherein said transition metal is selected from the group consisting of: Ag, Pt, Pd, Rh, Ru, Ir, Cu, Ni, Mo, Ti, V, Re and Mn.
- 31. The catalyst of claim 19, wherein said transition metal is selected from the group consisting of: Pt, Pd, Rh and Ru.
- 32. The catalyst of claim 19, wherein said transition metal salt, or complex thereof, is selected from the group consisting of: AgX; Ag(OTf); Ag(OTf)2; AgOAc; PtCl2; H2PtCl4; Pd2(DBA)3; Pd(OAc)2; PdCl2(RCN)2; (Pd(allyl)Cl)2; Pd(PR3)4; (Rh(NBD)2)X; (Rh (NBD)Cl)2; (Rh(COD)Cl)2; (Rh(COD)2)X; Rh(acac)(CO)2; Rh(ethylene)2(acac); (Rh(ethylene)2Cl)2; RhCl(PPh3)3; Rh(CO)2Cl2; RuHX(L)2(diphosphine), RuX2(L)2 (diphosphine), Ru(arene)X2(diphosphine), Ru(aryl group)X2; Ru(RCOO)2(diphosphine); Ru(methallyl)2(diphosphine); Ru(aryl group)X2(PPh3)3; Ru(COD)(COT); Ru(COD)(COT)X; RuX2(cymen); Ru(COD)n; Ru(aryl group)X2(diphosphine); RuCl2(COD); (Ru(COD)2)X; RuX2(diphosphine); RuCl2(═CHR)(PR13)2; Ru(ArH)Cl2; Ru(COD)(methallyl)2; (Ir (NBD)2Cl)2; (Ir(NBD)2)X; (Ir(COD)2Cl)2; (Ir(COD)2)X; CuX (NCCH3)4; Cu(OTf); Cu(OTf)2; Cu(Ar)X; CuX; Ni(acac)2; NiX2; (Ni(allyl)X)2; Ni(COD)2; MoO2(acac)2; Ti(OiPr)4; VO(acac)2; MeReO3; MnX2 and Mn(acac)2; wherein each R and R′ is independently selected from the group consisting of: alkyl or aryl; Ar is an aryl group; and X is a counteranion.
- 33. The catalyst of claim 32, wherein L is a solvent molecule and wherein said counteranion X is selected from the group consisting of: halogen, BF4, B(Ar)4, wherein Ar is fluorophenyl or 3,5-di-trifluoromethyl-1-phenyl, ClO4, SbF6, PF6, CF3SO3, RCOO and a mixture thereof.
- 34. The catalyst of claim 19, prepared in situ or as an isolated compound.
- 35. The catalyst of claim 19, wherein said transition metal salt, or a complex thereof is selected from the group consisting of: [Rh(COD)Cl]2, [Rh(COD)2]X, [Ir(COD)Cl]2, [Ir(COD)2]X, Rh(acac)(CO)2, Ni(allyl)X, Pd2(dba)3, [Pd(allyl)Cl]2, Ru(RCOO)2(diphosphine), RuX2(diphosphine), Ru(methylallyl)2(diphosphine) and Ru(aryl)X2(diphosphine), wherein X is selected from the group consisting of: BF4, ClO4, SbF6, CF3SO3, Cl and Br; and wherein said ligand is selected from the group consisting of compounds represented by the formula:
- 36. A process for preparation of an asymmetric compound comprising:
contacting a substrate capable of forming an asymmetric product by an asymmetric reaction and a catalyst prepared by a process comprising: contacting a transition metal salt, or a complex thereof, and a ligand selected from the group consisting of compounds represented by the formula or its enantiomer: 218wherein each X and X′ is independently selected from the group consisting of: alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR, halide, SiR3, P(O)R2, P(O)(OR)2 and P(OR)2; wherein each Z and Z′ is independently selected from the group consisting of: alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR, halide, SiR3, P(O)R2, P(O)(OR)2 and P(OR)2; or wherein Z and Z1 together form the bridging group A-B-A1; wherein each Z′, Z″, Z1′ and Z1″ is independently selected from the group consisting of: H, alkyl, aryl, substituted alkyl, substituted aryl, OR, SR, NR2, COOR, halide, SiR3, P(O)R2, P(O)(OR)2 and P(OR)2, or wherein Z′ and Z together form the bridging group A′-B-A; Z′ and Z together form a fused cycloaliphatic or aromatic group; Z1 and Z1′ together form the bridging group A1-B1-A1′; and/or Z1 and Z1′ together form a fused cycloaliphatic or aromatic group; wherein each A, A′, A1 and A1′ is independently selected from the group consisting of: O, CH2, NH, NR, S, CO and a bond; wherein each B and B1 is independently selected from the group consisting of: linear, branched or cyclic alkylene of 1 to 6 carbon atoms, arylene of 6 to 12 carbon atoms, O, CH2, NH, NR, S, CO, SO2, P(O)R, P(O)OR, POR, SiR2 and a bond; wherein each T is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, substituted aryl, alkoxide, aryloxide, R, R′, R″, YR′, YR″, Y′R′ and Y″R″; or wherein two T groups together form an alkylene, arylene, alkylenediamino, arylenediamino, alkelenedioxyl or arylenedioxyl; wherein each T′ is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, substituted aryl, alkoxide, aryloxide, R, R′, R″, YR′, YR″, Y′R′ and Y″R″; or wherein two T′ groups together form an alkylene, arylene, alkylenediamino, arylenediamino, alkelenedioxyl or arylenedioxyl; wherein each R, R′ and R″ is independently selected from the group consisting of: alkyl, substituted alkyl, aryl, aralkyl and alkaryl of 1 to 22 carbon atoms; or wherein two R groups, two R′ groups or two R″ group together form an alkylene or arelene group; and wherein each Y, Y′ and Y″ is independently selected from the group consisting of: O, CH2, NH, S and a bond between carbon and phosphorus; with the proviso that when the Y group at the 2′ position is a bond between carbon and phosphorus, X′ is hydrogen.
- 37. The process of claim 36, wherein said asymmetric reaction is selected from the group consisting of: hydrogenation, hydride transfer, allylic alkylation, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, olefin metathesis, hydrocarboxylation, isomerization, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition, epoxidation, kinetic resolution and [m+n] cycloaddition wherein m=3 to 6 and n=2.
- 38. The process of claim 37, wherein said transition metal is selected from the group consisting of:
Ag, Pt, Pd Rh, Ru, Ir, Cu, Ni, Mo, Ti, V, Re and Mn.
- 39. The process of claim 37, wherein said asymmetric reaction is hydrogenation and said substrate is selected from the group consisting of: imine, ketone, ethylenically unsaturated compound, enamine, enamide and vinyl ester.
- 40. The process of claim 37, wherein said asymmetric reaction is a silver-catalyzed asymmetric [3+2] cycloaddition of an azomethine ylide with a dipolarophile.
- 41. The process of claim 37, wherein said asymmetric reaction is a palladium-catalyzed allylic alkylation and said substrate is an allylic ester.
- 42. The process of claim 37, wherein said asymmetric palladium-catalyzed allylic alkylation reaction is a kinetic resolution reaction and said substrate is a racemic allylic ester.
- 43. The process of claim 37, wherein said asymmetric reaction is hydrogenation, said substrate is a beta-ketoester, said transition metal is Ru and said asymmetric compound is a beta-hydroxyester.
- 44. The process of claim 37, wherein said asymmetric reaction is hydrogenation, said substrate is an enamide, said transition metal is Ru and said asymmetric compound is a beta amino acid.
- 45. The process of claim 37, wherein said ligand is selected from the group consisting of compounds represented by the formula:
- 46. The process of claim 45, wherein said asymmetric reaction is hydrogenation, said substrate is a beta-ketoester, said transition metal is Ru and said asymmetric compound is a beta-hydroxyester.
- 47. The process of claim 45, wherein said asymmetric reaction is hydrogenation, said substrate is an enamide, said transition metal is Ru and said asymmetric compound is a beta amino acid.
Parent Case Info
[0001] This application claims priority from U.S. Provisional Application Serial No. 60/249,537, filed Nov. 17, 2000, and U.S. Provisional Application Serial No. 60/301,221, filed Jun. 27, 2001.
Provisional Applications (2)
|
Number |
Date |
Country |
|
60249537 |
Nov 2000 |
US |
|
60301221 |
Jun 2001 |
US |
Divisions (1)
|
Number |
Date |
Country |
Parent |
09991261 |
Nov 2001 |
US |
Child |
10660350 |
Sep 2003 |
US |