The rhodium-catalyzed diastereo- and enantioselective Michael addition of arylboronic acids to 3-alkylenyloxindoles has been developed with (R)-binap as a ligand. A wide variety of the desired functionalized oxindoles are smoothly obtained in high yields (up to 99%) with high enantioselectivities (up to 92% ee) and good diastereoselectivities (up to 82:18).

A new C2-symmetric chiral bis-sulfoxide ligand, (R,R)-1,2-bis(tert-butylsulfinyl)benzene, has been designed and prepared by the reaction of (R)-benzyl tert-butylsulfoxide with (R)-thiosulfinate. This ligand exhibits excellent enantioselectivities in the Rh-catalyzed asymmetric 1,4-addition reaction. In particular, the present work has realized access to optically pure flavanones for the first time through 1,4-addition of arylboronic reagents to chromenones.

A series of enantiomerically pure mono- and bis-aryl tert-butyl sulfoxides were synthesised to promote the enantioselective allylation of aldehydes with allyltrichlorosilane. Moderate to good yields and modest to high enantioselectivities were achieved. The absence of nonlinear effect, spacer effect, promoter loading and concentration effect indicate that only one molecule of aryl tert-butyl sulfoxide is involved in the stereodetermining step.

The asymmetric allylic alkylation of racemic 1,3-diphenyl-2-propenyl acetate 3 with dimethyl malonate proceeded smoothly in the presence of lithium acetate, BSA (N,O-bis(trimethylsilyl)acetamide), [Pd(η3-C3H5)Cl]2, and chiral tert-butanesulfinylphosphine ligand 2c to give the allylic alkylation product in good yield and high enantiomeric excess (up to 93% ee), while the enantioselectivities of allylic amination of 3 with various amines were moderate (up to 76% ee).(S,E)-Dimethyl 2-(1,3-diphenylallyl)malonateC20H20O4Ee = 93%[α]D25=-21.4 (c 1.40, CHCl3)Source of chirality: asymmetric allylic alkylationAbsolute configuration: (S,E)(R,E)-N-Benzyl-1,3-diphenylprop-2-en-1-amineC22H21NEe = 73%[α]D25=-7.6 (c 0.48, CHCl3)Source of chirality: asymmetric allylic aminationAbsolute configuration: (R,E)(R,E)-N-(1,3-Diphenylallyl)cyclohexanamineC21H25NEe = 70%[α]D25=-8.5 (c 0.46, CHCl3)Source of chirality: asymmetric allylic aminationAbsolute configuration: (R,E)(R,E)-4-(1,3-Diphenylallyl)morpholineC19H21NOEe = 76%[α]D25=-7.4 (c 0.34, CHCl3)Source of chirality: asymmetric allylic aminationAbsolute configuration: (R,E)(R,E)-1-(1,3-Diphenylallyl)pyrrolidineC19H21NEe = 52%[α]D25=-2.6 (c 1.0, CHCl3)Source of chirality: asymmetric allylic aminationAbsolute configuration: (R,E)(R,E)-1-(1,3-Diphenylallyl)piperidineC20H23NEe = 56%[α]D25=-11.7 (c 0.32, CHCl3)Source of chirality: asymmetric allylic aminationAbsolute configuration: (R,E)(R,E)-N,N-Dibenzyl-1,3-diphenylprop-2-en-1-amineC29H27NEe = 3%[α]D25=-2.9 (c 0.50, CHCl3)Source of chirality: asymmetric allylic aminationAbsolute configuration: (R,E)(R,E)-2-(1,3-Diphenylallyl)isoindoline-1,3-dioneC23H17NO2Ee = 55%[α]D25=-36.5 (c 0.50, CHCl3)Source of chirality: asymmetric allylic aminationAbsolute configuration: (R,E)(R,E)-tert-Butyl 4-(1,3-diphenylallyl)piperazine-1-carboxylateC24H30N2O2Ee = 73%[α]D25=-16.0 (c 0.50, CHCl3)Source of chirality: asymmetric allylic aminationAbsolute configuration: (R,E)

A series of enantiomerically pure mono- and bis-aryl tert-butyl sulfoxides were synthesised to promote the enantioselective allylation of aldehydes with allyltrichlorosilane. Moderate to good yields and modest to high enantioselectivities were achieved. The absence of nonlinear effect, spacer effect, promoter loading and concentration effect indicate that only one molecule of aryl tert-butyl sulfoxide is involved in the stereodetermining step.