S8 -Mediated Cyclization of 2-Aminophenols/thiophenols with Arylmethyl Chloride: Approach to Benzoxazoles and Benzothiazoles.

A metal-free approach to benzazoles from arylmethyl chlorides and 2-mercaptan/2-hydroxyanilines using elemental sulfur as a traceless oxidizing agent has been developed. The reactions proceeded in good to excellent yields, exhibiting good functional groups tolerance and gram-scale ability. A key mechanistic investigation indicated that the key intermediate trisulfide 6, which was characterized by NMR, HRMS and crystal X-ray crystallography, was separated in the reaction prior to the formation of the product.