Photochemical Nitrene Transfer Reactions of Iminoiodinanes with Sulfides

Abstract

Photochemical, metal-free nitrene transfer reactions for C−H amination, aziridination, or sulfilimination are highly desirable. Yet, photochemical sulfilimination reactions of nitrenes with sulfides are underdeveloped as singlet nitrene species would be required for a productive reaction. Herein, we describe the blue-light-mediated sulfilimination reaction using iminoiodinanes. We developed a protocol for a highly efficient stoichiometric reaction, which allows for the synthesis of sulfilimines in only 10 minutes reaction time. We further applied our reaction procedure towards allyl sulfides for the synthesis of sulfenamides in a sulfilimination/rearrangement cascade reaction. Moreover, we performed computational calculations and uncovered the participation of a singlet nitrene intermediate, which rapidly reacts with methyl phenyl sulfide to give the desired product.