Direct anti-Selective Catalytic Asymmetric Mannich-Type Reactions of α-Ketoanilides for the Synthesis of γ-Amino Amides and Azetidine-2-amides


  • We thank Z. Chen and H. Mihara at the University of Tokyo for helpful advice on this project, and T. Nitabaru and H. Morimoto for X-ray crystallography. This research was supported by Grants-in-Aid for Scientific Research (S), Scientific Research on Priority Areas (No. 20037010, Chemistry of Concerto Catalysis) (S.M.), and Young Scientists (A) (S.M.) from the JSPS and MEXT.


Breaking with convention: A homodinuclear nickel complex derived from a biphenyldiamine-based Schiff base catalyzed an anti-selective Mannich-type reaction of α-ketoanilides (see scheme) to afford unique building blocks for the synthesis of azetidine-2-amides and α-hydroxy γ-amino amides. This approach stands in contrast to conventional Mannich-type reactions for the synthesis of β-amino carbonyl compounds. o-Ns=o-nitrobenzenesulfonyl.

original image