Reductive thiolation and oxidative dehydroaromatization of cyclohexanones with primary amines and sodium sulfinates to access o-sulfanylanilines

Abstract

HI-promoted cascade reactions of cyclohexanones with primary amines and sodium sulfinates are described, providing an unprecedented method to access o-sulfanylanilines using cyclohexanones as an aryl source and sodium sulfinates as a sulfenylating reagent. Preliminary mechanistic studies revealed that three-component coupling begins with reductive ortho-thiolation of cyclic ketones with sulfinates and sequential condensation and dehydrogenative aromatization of in situ generated α-thiolated ketones with primary amines.