Visible light-mediated 1,3-acylative chlorination of cyclopropanes employing benzoyl chloride as bifunctional reagents in NHC catalysis

Chlorine-substituted ketones are essential intermediates in organic synthesis and commercially available benzoyl chloride participates in acyl chlorination, which provides an atom-and-step economic route for their synthesis. While atom-transfer radical addition (ATRA) is an efficient method for 1,2-acyl chlorination, achieving efficient 1,3-acyl chlorination remains a significant challenge. In this work, we developed an NHC/PC dual-catalyzed system for the 1,3-acyl chlorination of cyclopropanes using benzoyl chloride as a bifunctional reagent. Furthermore, it enables the synthesis of acyl-cyclopropanes featuring quaternary carbon centers through the nucleophilic annulation process. The practical utility of the approach is demonstrated by large-scale synthesis, product derivatization, and the preparation of analogs to antipsychotics such as haloperidol and melperone.