Electrochemically driven regioselective C-H phosphorylation of group 8 metallocenes

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. Metallocene-based phosphines are compounds with potential use in catalysis. Here, the authors report the electrochemical regioselective functionalization of group 8 metallocenes with phosphine oxides; over 60 examples of phosphorylated (benzo)ferrocenes and ruthenocenes can be accessed via this method without the need for a preinstalled directing group.

Automated summary

This study reports an electrochemically driven method for the efficient synthesis of phosphorylated metallocenes, providing guidance for the C-H functionalization of symmetric metallocenes.