Photoelectrocatalytic Cl-mediated C(sp3)–H aminomethylation of hydrocarbons by BiVO4 photoanodes

Interfacial photoelectrochemistry at photoanodes has been extensively researched for solar energy conversion, but its application for the production of high-value-added chemical compounds in organic chemistry still presents challenges. Herein, we report photoelectrocatalytic Cl-mediated C(sp³)-H aminomethylation of alkanes with self-developed and reusable BiVO₄ photoanodes. The swift condensation of aniline with aldehydes, along with the decrease of the electricity input of aniline by photogenerated holes in the BiVO₄ photoanodes, work together to prevent excessive oxidation of aniline, leading to high yields of the desired product. Mechanistic experiments demonstrate that Cl^- ions, as the key mediators, could be attracted to holes in the photoanodes and oxidized to form the Cl₂. This is followed by light-promoted homolytic cleavage of Cl₂, generating Cl radicals that efficiently abstract hydrogen atoms from hydrocarbons. This work opens an avenue for interfacial photoelectrochemical organic synthesis and demonstrates a potential method for optimizing solar energy conversion into fuels.