Claims
- 1. A ligand selected from the group consisting of compounds represented by I through XI:
- 2. The ligand of claim 1, wherein said ligand is a racemic mixture of enantiomers.
- 3. The ligand of claim 1, wherein said ligand is a non-racemic mixture of enantiomers.
- 4. The ligand of claim 1, wherein said ligand is one of the enantiomers.
- 5. The ligand of claim 1, having an optical purity of at least 85% ee.
- 6. The ligand of claim 1, having an optical purity of at least 95% ee.
- 7. The ligand of claim 1, wherein said ligand is supported on a support material.
- 8. The ligand of claim 7, wherein said support is selected from the group consisting of: a polymer support and an inorganic support.
- 9. The ligand of claim 8, wherein said polymer support is selected from the group consisting of polystyrene, polyacrylate, resin, polyethylene glycol, methoxy polyethylene glycol, dendritic polyester and dendritic polyenamide.
- 10. The ligand of claim 8, wherein said inorganic support is selected from the group consisting of: silica, alumina, zeolite and molecular sieve.
- 11. The ligand of claim 8, wherein said ligand is linked to a support material by a linker group selected from the group consisting of: NH(CH2)nSi(OEt)3, CO(CH2)nSi(OEt)3, (CH2)nSi(OEt)3, C—O, C—N and and NCF2 linker, wherein n=1 to 8.
- 12. The ligand of claim 1, including at least one water soluble functional group selected from the group consisting of: sulfonic, phosphoric and carboxylic.
- 13. A ligand selected from the group consisting of:
- 14. A ligand represented by the formula:
- 15. 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 I through XI:
- 16. The catalyst of claim 15, wherein said catalyst is a racemic mixture of enantiomers.
- 17. The catalyst of claim 15, wherein said catalyst is a non-racemic mixture of enantiomers.
- 18. The catalyst of claim 15, wherein said catalyst is one of the enantiomers.
- 19. The catalyst of claim 15, having an optical purity of at least 95% ee.
- 20. The catalyst of claim 15, wherein said transition metal is selected from the group consisting of: Pt, Pd, Rh, Ru, Ir, Cu, Ni, Mo, Ti, V, Re and Mn.
- 21. The catalyst of claim 15, wherein said transition metal is selected from the group consisting of: Pd, Rh, Ru and Ir.
- 22. The catalyst of claim 20, wherein said transition metal salt, or complex thereof, is selected from the group consisting of: PtCl2; Pd2(DBA)3; Pd(OAc)2; PdCl2(RCN)2; (Pd(allyl)Cl)2; (Rh(COD)Cl)2; (Rh(COD)2)X; Rh(acac)(CO)2; Rh(ethylene)2(acac); Rh(CO)2Cl2; Ru(RCOO)2(diphosphine); Ru(methylallyl)2(diphosphine); Ru(aryl group)X2(diphosphine); RuCl2(COD); (Rh(COD)2)X; RuX2(diphosphine); RuCl2(═CHR)(PR′3)2; Ru(ArH)Cl2; Ru(COD)(methylallyl)2; (Ir(COD)2Cl)2; (Ir(COD)2)X; Cu(OTf); Cu(OTf)2; Cu(Ar)X; CuX; NiX2; 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.
- 23. The catalyst of claim 22, wherein said counteranion X is selected from the group consisting of: halogen, BF4, B(Ar)4 wherein Ar is 3,5-di-trifluoromethyl-1-phenyl, ClO4, SbF6, CF3SO3, RCOO and a mixture thereof.
- 24. The catalyst of claim 15, prepared in situ or as an isolated compound.
- 25. A catalyst prepared by a process comprising: contacting a ruthenium salt, or a complex thereof, and a ligand represented by the formula:
- 26. 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 I through XI: 6970wherein X′ is selected from the group consisting of: alkyl, aryl, substituted alkyl, substituted aryl, hydroxy, alkoxy, aryloxy, siloxy, thioalkoxy, arylthio, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, amido, ester, reverse ester, keto, halo, silyl and SH; wherein R′ is selected from the group consisting of: alkyl, aryl, substituted alkyl, substituted aryl, hydroxy, alkoxy, aryloxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino and amido; wherein each X, Z and Z′ is independently selected from the group consisting of: O, NH, NR, CH2, CHR, CR2, C═O, S, SO2, and SO; wherein each Z″ is independently selected from the group consisting of: N, P, CH, and CR; wherein each R1, R2, R3 and R4 is independently selected from the group consisting of: H, alkyl, aryl, substituted alkyl, substituted aryl and OR; wherein each Y and Y′ is independently selected from the group consisting of: a diol protecting group residue, O, CO, C(OR)2, CH(OR), CH2, CHR, CR2, CR2, NR, SO2, —(CH2)n— wherein n is 0 or an integer from 1 to 8, —(CH2)nQ(CH2)m— wherein each n and m is independently an integer from 1 to 8, divalent phenyl, substituted divalent phenyl, 2,2′-divalent-1,1′-biphenyl, substituted 2,2′-divalent-1,1′-biphenyl, 2,2′-divalent-1,1′-binaphthyl, substituted 2,2′-divalent-1,1′-binaphthyl, 1,1′-ferrocene, substituted 1,1′-ferrocene, wherein the substituent in each of said substituted divalent phenyl, biphenyl, binaphthyl and ferrocene is one or more moiety each independently selected from the group consisting of: alkyl, aryl, aralkyl, alkaryl, alkenyl, akkynyl, F, Cl, Br, I, OH, OR, SH, SR, COOH, COOR, SO3H, SO3R, PO3H2, PO3HR, PO3R2, NH2, NHR, NR2, PR2, AsR2, SbR2 and nitro; and wherein each R is independently selected from the group consisting of: alkyl aryl, substituted alkyl, substituted aryl, fluoroalkyl, perfluoroalkyl and —CR′2(CR′2)qQ(CR′2)pR′ wherein each q and p is independently an integer from 1 to 8, Q is selected from the group consisting of: O, S, NR, PR, AsR, SbR, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocycle and divalent fused heterocycle.
- 27. The process of claim 26, wherein said asymmetric reaction is selected from the group consisting of: hydrogenation, hydride transfer, allylic alkylation, hydrosilylation, hydroboration, hydrovinylation, hydroformylation, hydrocarboxylation, isomerization, cyclopropanation, Diels-Alder reaction, Heck reaction, isomerization, Aldol reaction, Michael addition and epoxidation.
- 28. The process of claim 27, 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.
- 29. The process of claim 27, wherein said substrate is an electron-rich substrate.
- 30. The process of claim 26, wherein said catalyst is an Rh complex of (R,S,S,R)-DIOP*.
- 31. The process of claim 26, wherein said catalyst is an Rh complex of
- 32. A process for preparing a ligand enantiomer comprising the steps of:
contacting an enantiomer of tartaric acid diester and a diol protecting group in the presence of an acid catalyst to produce a bis-protected tartrate diester; contacting said bis-protected tartrate diester and a reducing agent to convert the ester functional groups in said tartaric acid diester to a diol; converting said diol to a sulfonate ester; and displacing the sulfonate group in said sulfonate ester with lithium diphenylphosphinide to produce ligand enantiomer.
Parent Case Info
[0001] This application claims priority from Provisional Application Serial Nos. 60/164,508 filed on Nov. 10, 1999 and 60/187,851 filed on Mar. 8, 2000.
Provisional Applications (2)
|
Number |
Date |
Country |
|
60164508 |
Nov 1999 |
US |
|
60187851 |
Mar 2000 |
US |
Divisions (1)
|
Number |
Date |
Country |
Parent |
09711635 |
Nov 2000 |
US |
Child |
10410711 |
Apr 2003 |
US |