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

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:
• 59 60
• wherein 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, OK OR, SH, SR, COOH, COOR, SO3I, 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.

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:
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• wherein 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, L 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.

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.