Organoelectrocatalysis Enables Direct Cyclopropanation of Methylene Compounds

Cyclopropane is a prevalent structural unit in natural products and bioactive compounds. While the transition metal-catalyzed alkene cyclopropanation of functionalized compounds such as a-diazocarbonyl derivatives has been well established and provides straightforward access to cyclopropanes, cyclopropanation directly from the more stable and simpler methylene compounds has remained an unsolved challenge despite the highly desirable benefits of minimal prefunctionalization and increased operational safety. Herein we report an electrocatalytic strategy for the cyclopropanation of active methylene compounds, employing an organic catalyst. The method shows a broad substrate scope and excellent scalability, requires no metal catalyst or external chemical oxidant, and provides convenient access to several types of cyclopropanefused heterocyclic and carbocyclic compounds. Mechanistic investigations suggest that the reactions proceed through a radicalpolar crossover process to form the two new carbon-carbon bonds in the nascent cyclopropane ring.

Automated summary

This study presents an electrocatalytic strategy for the cyclopropanation of active methylene compounds using an organic catalyst, which eliminates the need for transition metal catalysts and external chemical oxidants. The method shows a broad substrate scope and excellent scalability, allowing for the convenient synthesis of various types of cyclopropane-fused heterocyclic and carbocyclic compounds.