Efficient Synthesis of Sulfenamides through Mitsunobu‐type Coupling Reaction of Thiols with Amines using Dibenzyl Azodicarboxylate

Abstract S−H activation reaction of thiols employing dibenzyl azodicarboxylate (DBAD) has been developed for the preparation of sulfenamides. The dehydrogenation of thiols and amines under these reaction conditions involved the formation of dibenzyl hydrazine‐1,2‐dicarboxylate ( 5 a ), which led to the S−N bond formation reaction. The reaction proceeds efficiently with the release of 5 a and affords various sulfenamides in good to excellent yields.