Walking Cations: Transition‐Metal Free Benzyl Cation‐Triggered sp2 C—H Phosphorylation and Etherification

Abstract

Comprehensive SummaryA novel benzyl cation‐triggered site‐selective sp2 C—H phosphorylation and etherification was developed. This reaction was conducted under the transition metal‐free conditions through cation migration via dearomatization. Under the reaction conditions, the derivatives of naphthalenes, benzofurans and benzo[b]thiophenes all can be transformed into the corresponding products in good to excellent yields. It provides a method to construct sp2 C—P and sp2 C—O bonds as well as a new strategy for benzylic activation‐triggered sp2 C—H functionalization.