A concise and efficacious benzotriazole-mediated novel two-step protocol has been developed for easy access to glycoconjugate benzothiazoles from protected carbohydrates. The benzotriazolemethanethione 3, prepared by the reaction of free alcohol with bis(1H-benzo[1,2,3]triazol-1-yl)methanethione, on treatment with silanes or stannane under heating or microwave irradiation undergoes free radical β-scission of N-N bond and affords diverse range of 2-O-substituted benzothiazoles 4 via cyclative elimination of molecular nitrogen. The structures of all of the compounds have been elucidated using IR, NMR, MS, and elemental analysis, and five of them have been characterized by single-crystal X-ray analysis.

A novel, one-pot, and highly facile protocol has been devised for an easy access of a series of novel glycosyl carboxamides from aldehydes using diacetoxyiodobenzene in the presence of ionic liquid at ambient temperature.

The synthesis of numerous 2-N/S/C-substituted benzothiazoles was achieved from substituted thiocarbonylbenzotriazoles via free-radical intramolecular cyclative cleavage of the benzotriazole ring in the presence of (TMS)3SiH and AIBN under mild conditions. The developed methodology demonstrates significant compatibility under microwave conditions and is important as it avoids the use of toxic metals for radical cyclization.

A Lewis-acid-mediated ring cleavage of acylbenzotriazoles (RCOBt) followed by cyclization to corresponding benzoxazoles was achieved in good to excellent yields. The reaction was found consistent with the milligram to gram scale.

An attempt of Bu3SnH mediated cyclization of acylbenzotriazoles (RCOBt) to corresponding benzoxazole failed; instead, corresponding N‐phenylamides were achieved in good yield. The reactions proceed via reductive cleavage of benzotriazole ring with consequent evolution of molecular nitrogen (N2). A diverse range of amide has been achieved in high yields. Structures of all the compounds have been elucidated using IR, MS, 1H and 13C NMR, while four of them (3 o, 3 w, 4 and 5) have also been characterized by single crystal X‐ray analysis.