Catalytic Intramolecular Ketone Haloacylation Enabled Stereoselective Heterolytic Cleavage of Cyclopropyl Ketones with Enhanced Reactivity and Regioselectivity beyond Electronics.

Abstract

By integration of oxocarbenium activation and Lewis acid coordination activation via conformational proximity-driven, Pd(II)- or Cu(I)-catalyzed intramolecular ketone haloacylation, regio- and stereoselective heterolytic ring-opening 1,5-haloacylation of cyclopropyl ketones, including those with weak single alkyl donors, has been developed for the synthesis of valuable α-quaternary halo-γ-butenolides. The vicinal carboxylic acid and ketone acceptors are no longer just spectator activators. Further, this reaction delivers a constant regioselectivity regardless of the electronic nature of substituents, even the malonate.