Photo-induced versatile aliphatic C-H functionalization via electron donor-acceptor complex

The ability to selectively introduce diverse functionality onto hydrocarbons is of substantial value in the synthesis of both small molecules and pharmaceuticals. In this endeavour, as a photocatalyst- and metal-free process, the electron donor-acceptor (EDA) strategy has not been well explored. Here we report an approach to aliphatic carbon-hydrogen bond diversification through an EDA complex constituted by HCl and S^IV=O groups. As an efficient hydrogen atom transfer (HAT) reagent, chlorine radical can be produced via a proton-coupled electron transfer process in this system. Based on this unusual path, a photo-promoted versatile aliphatic C-H functionalization is developed without photo- and metal-catalysts, including thiolation, arylation, alkynylation, and allylation. This conversion has concise and ambient reaction conditions, good functional group tolerance, and substrate diversity, and provides an alternative solution for the high value-added utilization of bulk light alkanes.