The copper-catalyzed enantioselective conjugate addition of diethylzinc to acyclic enones was achieved with chiral sulfoxide–phosphine (SOP) ligands. This process showed good functional group tolerance and gave the 1, 4-adducts with excellent enantioselectivities (up to 96% ee).

A cooperative Cu/Pd-catalyzed asymmetric three-component reaction of styrenes, B2(pin)2, and allyl carbonates was reported. This reaction, in the presence of chiral CuOAc/SOP and achiral Pd(dppf)Cl2 catalysts, occurs smoothly with high enantioselectivities (up to 97% ee) . The allylboration products, which contain alkene (or diene) unite and alkylboron group, are easily functionalized. The utility of this protocol was demonstrated through the synthesis of an antipsychotic drug, (−)-preclamol.

Highly efficient and enantioselective copper(I)-catalyzed pinacolboryl addition of N-Boc-imines is reported. By using a single chiral sulfoxide-(dialkyl)phosphine (SOP) ligand, both enantiomeric isomers of α-amino boronic esters were obtained through an achiral counteranion switch.

Rh-Catalyzed asymmetric 1,4-selective addition of arylboronic acids to β,γ-unsaturated α-keto ester was developed using chiral tert-butanesulfinylphosphine as ligand, good yields (up to 87%), good 1,4-regioselectivities (up to 96:4), and high enantioselectivities (up to 94% ee) were achieved.

The transition metal-catalyzed asymmetric variant of the title reaction is normally limited to N-protected isatins. However, Rh(I)/chiral sulfoxide phosphine complexes were found to catalyze the enantioselective addition of arylboronic acids to NH isatins under mild conditions. A variety of chiral 3-aryl-3-hydroxyl-2-oxindoles were obtained with high yields and with good to excellent enantioselectivities (85–92% ee)..(R)-1-Benzyl-3-hydroxy-3-phenylindolin-2-oneC21H17NO2[α]D20=+37 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-3-Hydroxy-1-methyl-3-phenylindolin-2-oneC15H13NO2[α]D20=+65 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-3-Hydroxy-1-(4-nitrobenzyl)-3-phenylindolin-2-oneC21H16N2O4[α]D20=+19 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)3-Hydroxy-1-(4-methoxybenzyl)-3-phenylindolin-2-oneC22H19NO3[α]D20=+22 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-3-Hydroxy-3-phenylindolin-2-oneC14H11NO2[α]D20=-10 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-5-Chloro-3-hydroxy-3-phenylindolin-2-oneC14H10ClNO2[α]D20=-68 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-5-Fluoro-3-hydroxy-3-phenylindolin-2-oneC14H10FNO2[α]D20=+7 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-3-Hydroxy-5-methyl-3-phenylindolin-2-oneC15H13NO2[α]D20=-50 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-5-Chloro-3-hydroxy-3-o-tolylindolin-2-oneC15H12ClNO2[α]D20=+28 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-5-Chloro-3-hydroxy-3-m-tolylindolin-2-oneC15H12ClNO2[α]D20=-67 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-5-Chloro-3-hydroxy-3-(3-methoxyphenyl)indolin-2-oneC15H12ClNO3[α]D20=-55 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-5-Chloro-3-hydroxy-3-(4-methoxyphenyl)indolin-2-oneC15H12ClNO3[α]D20=-116 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphine Absolute configuration: (R)(R)-5-Chloro-3-(4-fluorophenyl)-3-hydroxyindolin-2-oneC14H9ClFNO2[α]D20=-80 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-5-Chloro-3-hydroxy-3-p-tolylindolin-2-oneC15H12ClNO2[α]D20=-86 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-3-(4-tert-Butylphenyl)-5-chloro-3-hydroxyindolin-2-oneC18H18ClNO2[α]D20=-82 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-3-(4-(Benzyloxy)phenyl)-5-chloro-3-hydroxyindolin-2-oneC21H16ClNO3[α]D20=-83 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-5-Chloro-3-(3,5-dimethylphenyl)-3-hydroxyindolin-2-oneC16H14ClNO2[α]D20=-75 (c 0.1, MeOH)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-chloro-3-hydroxy-3-phenylindolin-2-oneC21H16ClNO2[α]D20=+6 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-fluoro-3-hydroxy-3-phenylindolin-2-oneC21H16FNO2[α]D20=+57 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-3-hydroxy-5-methyl-3-phenylindolin-2-oneC22H19NO2[α]D20=+17 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-chloro-3-hydroxy-3-o-tolylindolin-2-oneC22H18ClNO2[α]D20=+98 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-chloro-3-hydroxy-3-m-tolylindolin-2-oneC22H18ClNO2[α]D20=+9 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-chloro-3-hydroxy-3-(3-methoxyphenyl)indolin-2-oneC22H18ClNO3[α]D20=+16 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-chloro-3-hydroxy-3-(4-methoxyphenyl)indolin-2-oneC22H18ClNO3[α]D20=-43 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-chloro-3-(4-fluorophenyl)-3-hydroxyindolin-2-oneC21H15ClFNO2[α]D20=-13 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-chloro-3-hydroxy-3-p-tolylindolin-2-oneC22H18ClNO2[α]D20=-22 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-3-(4-tert-butylphenyl)-5-chloro-3-hydroxyindolin-2-oneC25H24ClNO2[α]D20=-23 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-3-(4-(benzyloxy)phenyl)-5-chloro-3-hydroxyindolin-2-oneC28H22ClNO3[α]D20=-45 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)(R)-1-Benzyl-5-chloro-3-(3,5-dimethylphenyl)-3-hydroxyindolin-2-oneC23H20ClNO2[α]D20=+13 (c 0.1, CHCl3)Source of chirality: (R)-(6-(tert-butylsulfinyl)-2,3-dimethoxyphenyl)diphenylphosphineAbsolute configuration: (R)

Efficient Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to ethyl-γ-phthalimidocrotonate by using bis-sulfoxide ligand affords γ-aminobutyric acid (GABA) derivatives with high enantioselectivities (90–96% ee) under mild conditions. Optically pure (S)-Baclofen and (S)-Rolipram have been prepared successfully through this synthetic route.

A class of novel chiral SO–S-type bidentate ligands based on the tert-butylsulfinyl moiety as the sole chiral source were designed and synthesized through a simple and efficient pathway. These ligands are effective catalyst precursors for the palladium-catalyzed allylic alkylation of 1,3-diphenyl-2-propenyl acetate and moderate to good stereoselectivities (up to 84% ee) were obtained.(R)-(2-(tert-Butylsulfinyl) phenyl) (phenyl) sulfaneC16H18OS2[α]D20=+244.6 (c 0.8, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-(2-(tert-Butylsulfinyl) phenyl) (methyl) sulfaneC11H16OS2[α]D20=+286.3 (c 1.0, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-tert-Butyl (2-(tert-butylsulfinyl) phenyl) sulfaneC14H22OS2[α]D20=+191.4 (c 1.1, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-Benzyl (2-(tert-butylsulfinyl) phenyl) sulfaneC17H20OS2[α]D20=+207.3 (c 0.5, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-(2-(tert-Butylsulfinyl) phenyl) (naphthalene-1-ylmethyl) sulfaneC21H22OS2[α]D20=+269.3 (c 1.0, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-(2-(tert-Butylsulfinyl) phenyl) (2,4,6-trimethylbenzyl) sulfaneC20H26OS2[α]D20=+206.6 (c 1.0, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-Benzyl (2-(tert-butylsulfinyl)-3-methoxyphenyl) sulfaneC18H22O2S2[α]D20=+70.2 (c 1.5, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-Benzyl (2-(tert-butylsulfinyl)-6-methoxyphenyl) sulfaneC18H22O2S2[α]D20=-35.4 (c 0.8, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-Benzyl (2-(tert-butylsulfinyl)-6-isopropoxyphenyl) sulfaneC20H26O2S2[α]D20=-66.1 (c 0.7, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-Benzyl (2-(tert-butylsulfinyl)-6-(methoxymethoxy) phenyl) sulfaneC19H24O3S2[α]D20=-17.1 (c 0.7, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(R)-Benzyl (2-(tert-butylsulfinyl)-3, 6-dimethoxyphenyl) sulfaneC19H24O3S2[α]D20=-15.3 (c 0.7, CH2Cl2)Source of chirality: (R)-tert-butyl tert-butanethiosulfinateAbsolute configuration: (R)(S,E)-Dimethyl 2-(1,3-diphenylallyl) malonateC20H20O4[α]D20=-14.6 (c 0.7, EtOH) 84%eeSource of chirality: asymmetric synthesisAbsolute configuration: (S)(S,E)-Diethyl 2-(1,3-diphenylallyl) malonateC22H24O4[α]D20=-15.5 (c 0.8, CHCl3) 81%eeSource of chirality: asymmetric synthesisAbsolute configuration: (S)(S,E)-Dibenzyl 2-(1,3-diphenylallyl) malonateC32H28O4[α]D20=-7.2 (c 0.4, CHCl3) 74%eeSource of chirality: asymmetric synthesisAbsolute configuration: (S)(E)-Ethyl 2-cyano-3,5-diphenylpent-4-enoateC20H18NO2[α]D20=-4.2 (c 0.3, CHCl3) 79%eeSource of chirality: asymmetric synthesisAbsolute configuration: undetermined