Photochemical halogen-bonding assisted carbothiophosphorylation reactions of alkenyl and 1,3-dienyl bromides.

Herein, we present a synthetic procedure for the facile and general preparation of novel -alkenyl and dienyl phosphoro(di)thioates for the first time. Extensive mechanistic investigations support that the reactions rely on a photochemical excitation of a halogen-bonding complex, formed with a phosphorothioate salt and an alkenyl or dienyl bromide, which light-induced fragmentation leads to the formation of the desired products through a radical-based pathway. The substrate scope is broad and exhibits a wide functional group tolerance in the formation of the final compounds, including molecules derived from natural products, all with unknown and potentially interesting biological properties.