Electrochemically driven regioselective C-H phosphorylation of group 8 metallocenes.

Zheng, Hao; Liu, Chang-Hui; Guo, Shi-Yu; He, Gu-Cheng; Min, Xiang-Ting; Zhou, Bo-Chao; Ji, Ding-Wei; Hu, Yan-Cheng et al. · Nat Commun · 2022

basic_science · Level V

Where this comes from

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.