Electrochemically driven regioselective C−H phosphorylation of group 8 metallocenes
Hao Zheng, Changhui Liu, Shiyu Guo, Gu‐Cheng He, Xiang‐Ting Min, Bo‐Chao Zhou, Ding‐Wei Ji, Yan‐Cheng Hu, Qing‐An Chen
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.