Electrochemically driven regioselective C−H phosphorylation of group 8 metallocenes

Abstract

Metallocenes are privileged backbones for synthesis and catalysis. However, the direct dehydrogenative C−H functionalization of unsymmetric metallocenes suffers from reactivity and selectivity issues. Herein, we report an electrochemically driven regioselective C−H phosphorylation of group 8 metallocenes. Mechanistic investigations indicate this dehydrogenative cross coupling occurs through an electrophilic radical substitution of the metallocene with a phosphoryl radical, facilitated by the metallocene itself. This work not only offers an efficient and divergent synthesis of phosphorylated metallocenes, but also provides a guide to interpret the reactivity and regioselectivity for the C−H functionalization of unsymmetric metallocenes.