Asymmetric disulfonimide-catalyzed synthesis of δ-amino-β-ketoester derivatives by vinylogous Mukaiyama-Mannich reactions

Abstract

An organocatalytic asymmetric synthesis of δ-amino-β-ketoester derivatives has been developed. A chiral disulfonimide (DSI) serves as a highly efficient precatalyst for a vinylogous Mukaiyama-Mannich reaction of readily available dioxinone-derived silyloxydienes with N-Boc-protected imines, delivering products in excellent yields and enantioselectivities. The synthetic utility of this reaction is illustrated in various transformations, including a new CC bond-forming reaction, which provide useful enantioenriched building blocks. The methodology is applied in a formal synthesis of (-)-lasubin.

Keywords: disulfonimides; organocatalysis; vinylogous Mukaiyama-Mannich reaction; δ-amino-β-ketoesters.