An efficient kinetic resolution of racemic trans-2,3-aziridinyl alcohols is established via zinc catalyzed ring opening reactions with various amines as the nucleophiles. The directing effect of the hydroxyl group and the precise enantiodiscrimination by dinuclear zinc cooperative catalyst are the keys to success of high regioselectivity and enantioselectivity. A range of enantioenriched vicinal diamines and trans-2,3-aziridinyl alcohols were obtained in good yields with excellent ee values. To the best of our knowledge, this is the first example of directed enantioselective nucleophilic ring opening reactions of 2,3-aziridinyl alcohols.

An efficient approach to saccharin-fused 1,4-DHPs has been established by using a [3 + 3] annulation process. The chemical event was enabled by a Et 3 N-catalyzed tandem Michael/aza-Pinner reaction of alkyl cyclic N-sulfonyl ketimines as nucleophiles with α,α-dicyanoolefins. Under mild conditions, the desired products were readily prepared in good to excellent yields and with broad functional group tolerance (up to 95 % yield, 29 examples). Notably, this practical methodology features the synthesis of pentacyclic spirooxindoles bearing a quaternary spiro-stereocenter.[a] Z.

We report herein an enantioselective acyl transfer protocol via electrophile activation. The reaction cascade sequence encompasses dinuclear zinc-catalyzed asymmetric Michael addition, intramolecular cyclization, and retro-Claisen reaction, which leads to a step- and atom-economic approach to a variety of protected cyclic tertiary α-hydroxyketones in good yields with excellent enantioselectivities (24 examples, 56%-82% yield, 1.5-13 dr and 79%-96% ee). Besides, the large-scale synthesis and further transformation of the products demonstrate the effectiveness of this method for organic synthesis.