Synthesis of Sulfenamides from Benzoazole‐2‐thiones with Primary and Secondary Amines using Triphenylbismuth Dichloride‐Mediated S−N Bond Formation Reaction

Abstract

A novel and efficient method for the synthesis of sulfenamides with an S–N bond, which have attracted attention as industrial reagents and biologically active substances, is described herein. The reactions of benzoazole‐2‐thiones with various primary or secondary amines in the presence of triphenylbismuth dichloride at 60 °C in DMSO under aerobic conditions afforded the corresponding sulfenamides in moderate‐to‐excellent yields. This reaction is the first example of an efficient S–N bond formation reaction utilizing a low‐toxicity pentavalent organobismuth reagent under mild reaction conditions. The reaction will likely be applied to develop bioactive compounds with medicinal value or compounds with industrial utility.