Oxidation-Triggered Single-Carbon Atom Doping into Acyl Chlorides Using N -Isocyanide

Abstract

Atomic carbon is an attractive intermediate because it can form four new covalent bonds in a single transformation, but its synthetic use is limited by its short lifetime. Herein, we report an oxidation-triggered carbon-atom insertion into acyl chlorides using bench-stable N-isocyaniminophosphorane (PINC). Unlike our previous thermal/Rh-catalyzed protocol, this method proceeds at room temperature to afford cyclic α-chloro ketones. Mechanistic studies support oxidation-induced diazo formation from a phosphazine intermediate, followed by carbene generation.