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

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 sketelon 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.