Organocatalytic enantioselective desymmetrization of enal-tethered cyclohexane-1,3-diones

Abstract

Organocatalytic asymmetric desymmetrization of prochiral cyclohexane-1,3-diones has been demonstrated through the merging of iminium and enamine activation. The tandem annulation reaction proceeds through a sequential oxa-Michael addition/intramolecular aldol reaction/[1,3]-amino oxetane rearrangement pathway. Mechanistic study using an ¹⁸O-water experiment suggests oxetane rearrangement instead of direct dehydration. The formation of other competing Rauhut–Currier products via alkoxy-elimination was not observed.