Synthesis of Polysubstituted Bicyclo[3.1.0]Hexanes via Boronyl Radical Catalyzed [3 + 2] Cycloaddition of Cyclopropanes with Cyclopropenes

Abstract Bicyclo[3.1.0]hexane is a key structural unit in numerous natural products and small molecule drugs. The efficient and sustainable construction of this skeleton is of particular importance. Herein, we report a boronyl radical‐catalyzed [3 + 2] cycloaddition reaction of cyclopropanes and cyclopropenes for the synthesis of polysubstituted bicyclo[3.1.0]hexanes. This reaction proceeds under metal‐free conditions and can rapidly construct multiple carbon─carbon bonds, exhibits atom economy and operational simplicity, and demonstrates good substrate applicability and excellent functional group tolerance.