Chiral phosphines, transition metal complexes thereof and uses thereof in asymmetric reactions

A ligand selected from the group consisting of compounds represented by A through Z, AA, BB and CC:

• wherein “bridge 1” is selected from the group consisting of:
• C═O, C═S, SO2, PO(OR1), PO(NHR1), PO(NR1R2), 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, SiR12 (CH2)n where n is an integer ranging from 1 to 8, and (CR22)nX1(CR22)m wherein each n, m is independently an integer from 1 to 8, wherein X1 is selected from the group consisting of:
• O, S, NR3, PR32, +NR32, +PR32, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group and divalent fused heterocyclic group;
• wherein “bridge 2” is selected from the group consisting of:
• NH, O, a single bond, (CH2)n, O(CH2)nO, NH(CH2)nNH, wherein each n is independently an integer from 1 to 8, divalent phenyl, substituted divalent phenyl, divalent phenyl amine, substituted divalent phenyl amine, 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, O(CR22)nX1(CR22)mO, NH(CR22)nX1(CR22)mNH and (CR22)nX1(CR22)m wherein each n, m is independently an integer from 1 to 8, wherein X1 is selected from the group consisting of:
• O, S, NR3, PR32, +NR32, +PR32, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group and divalent fused heterocyclic group;
• wherein “bridge 3” is selected from the group consisting of:
• SO2, CO, COCO, OC(CH2)nCO, (CH2)n wherein n is an integer ranging from 1 to 8, COArCO, wherein Ar is selected from the group consisting of:
• 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 and CO(CR22)nX1(CR22)mCO wherein each n, m is independently an integer from 1 to 8, wherein X1 is selected from the group consisting of:
• O, S, NR3, PR32, +NR32, +PR32, divalent aryl, divalent fused aryl, divalent 5-membered ring heterocyclic group and divalent fused heterocyclic group;
• wherein each R1 is independently selected from the group consisting of:
• aryl, alkyl, alkaryl, aralkyl and substituted derivatives thereof wherein the substituent in said substituted derivatives is selected from the group consisting of:
• carboxylic acid, alkoxy, hydroxy, alkylthio, thiol and dialkylamino;
• wherein each R2 and R3 is independently selected from the group consisting of:
• aryl, alkyl, substituted aryl and substituted alkyl group;
• wherein each said substituted divalent phenyl, divalent phenyl amine, biphenyl, binaphthyl and ferrocene derivative comprises at least one substituent selected from the group consisting of aryl, substituted aryl, alkyl, heteroatom, F, Cl, Br, I, COOR1, SO3R1, PO3R12, OR1, SR1, PR12, AsR12, SbR12, OAr, nitro, amino, vinyl, substituted vinyl and sulfonic acid;
• wherein each R and R′ is independently selected from the group consisting of:
• aryl, alkyl, alkaryl, aralkyl and substituted derivatives thereof, wherein the substituent in said substituted derivatives is selected from the group consisting of:
• carboxylic acid, alkoxy, hydroxy, alkylthio, thiol, dialkyl amino groups;
• wherein each X and X′ is independently selected from the group consisting of:
• aryl, alkyl, alkaryl, aralkyl, alkoxy, alkoxy, hydroxy, alkylthio, thiol, primary amine, secondary amine and ArNH;
• wherein each Z and Z′ is independently selected from the group consisting of:
• hydrogen, halogen, alkyl, aryl, aryloxy, nitro, amino, vinyl, substituted vinyl and sulfonic acid;
• and
• wherein each Q, Q′, Y, Y′, T and T′ is independently selected from the group consisting of:
• aryl, alkyl, alkaryl, aralkyl and substituted derivatives thereof, wherein the substituent in said substituted derivatives is selected from the group consisting of:
• carboxylic acid, alkoxy, hydroxy, alkylthio, thiol and dialkylamino.