Copper-Catalyzed Radical Aminocyanation of Allenes

Abstract

The aminocyanation of allenes remains an uncharted territory in organic synthesis, despite the significant progress in aminocyanation of other unsaturated hydrocarbons. Current amination strategies for allenes suffer from limitations such as stringent pre-functionalization requirements, costly catalysts and narrow substrate scope. Herein, we report a copper-catalyzed three-component aminocyanation of allenes using N-halobenzenesulfonimides and trimethylsilyl cyanide, achieving simultaneous installation of amine and cyano groups with high regioselectivity. The copper catalyst synergistically facilitates N−X bond homolysis to generate nitrogen-centered radicals and activates cyanide sources, while enabling efficient reaction progression by generating coordination intermediates and radical cations. This work establishes a novel copper-catalyzed strategy for the aminocyanation of allenes, which overcomes key limitations of existing strategies by achieving broad substrate generality without pre-functionalization and offering cost-effective practicality through a copper-catalyzed radical cascade method.