Photo-induced catalytic halopyridylation of alkenes

The Mizoroki-Heck reaction and its reductive analogue are staples of organic synthesis, but the ensuing products often lack a chemical handle for further transformation. Here we report an atom-economical cross-coupling of halopyridines and unactivated alkenes under photo-redox catalysis to afford a series of alkene halopyridylation products. This protocol with mild and redox neutral conditions contributes broad substrate scope. As a complement to conventional Heck-type reaction, this radical process avoids the involvement of β-H elimination and thus useful pyridyl and halide groups could be simultaneously and regioselectively incorporated onto alkenes. The success depends on TFA-promoted domino photocatalytic oxidative quenching activation and radical-polar crossover pathway. Plausible mechanism is proposed based on mechanistic investigations. Moreover, the reserved C−X bonds of these products are beneficial for performing further synthetic elaborations.

Shi-Yu Guo, Fan Yang, Ting-Ting Song, Yu-Qing Guan, Xiang-Ting Min, Ding-Wei Ji, Yan-Cheng Hu, Qing-An Chen