TEMPO-Catalyzed Aerobic Oxidative Coupling of Thiols for Metal-Free Formation of S-N/S-S Bonds

Catalytic syntheses of organic sulfenamides and disulfides have great significance and value in synthetic chemistry and bioscience. To establish a versatile and efficient technology for such reactions, an aerobic oxidative coupling method for the formation of S-N and S-S bonds, using TEMPO as a catalyst and O-2 as an oxidant, has been successfully developed. Reactions showed good tolerance toward various amines and thiols. Sulfenamides were produced in up to 99% yield, while disulfides were formed in up to 97% yield in one-pot syntheses. Activation of the N-H bond by 2,2-disbenzothiazoledisulfide showed the great potential in organic synthesis.