An efficient and convenient α-hydroxyallylation approach for the asymmetric synthesis of a variety of β-amino-α-vinyl alcohols has been successfully developed. A wide range of vinylic amino alcohol derivatives could be obtained in very good yields and with excellent diastereomeric ratios of up to 99:1 in favor of anti isomers by highly diastereoselective Zn-promoted benzoyloxyallylation of chiral N-tert-butanesulfinyl imines with 3-bromopropenyl benzoate at room temperature. In particular, excellent enantioinduction of the two new stereogenic centers was observed, with up to 98 % ee. The method provides a new route for the direct α-hydroxyallylation of imines in a highly stereoselective manner. Moreover, the synthetic value of the method has also been demonstrated by the most concise and straightforward synthesis of (−)-cytoxazone yet reported.

The synthesis of a new type of C₂-symmetric chiral diene ligands with a nonbridged bicyclic [3.3.0] backbone was successfully introduced. Using highly efficient lipase-catalyzed transesterification and Suzuki-coupling strategies, a broad family of enantiopure 3,6-disubstituted bicyclo[3.3.0] dienes with different electronic and steric properties could be easily prepared. The application of these new diene ligands in the Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds have been examined, and excellent enantioselectivities (up to 98 % ee) as well as good yields are achieved under very mild reaction conditions at room temperature.