Photoinduced Sulfanyloximation of Styrenes Using N-Nitrosamines and Thiols

Abstract

Molecules featuring both sulfur and nitrogen atoms are privileged scaffolds in medicinal chemistry and biological systems. However, methods for the direct and regioselective installation of these heteroatoms onto alkenes remain limited. Herein, we report a visible-light-induced, three-component sulfanyloximation of styrenes utilizing thiols and N-nitrosamine as a bench-stable nitrogen oxide (NO) surrogate. This regioselective protocol operates under mild conditions with remarkable functional group tolerance. The synthetic utility of this methodology is further demonstrated by its extension to the synthesis of 2,3-disubstituted indoles and the divergent downstream derivatization of α-sulfanyl ketoxime products via imidoyl fluoride intermediates. An extensive mechanistic investigation supports a pathway initiated by thiyl radical addition to alkenes followed by radical coupling with in situ generated NO.