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Site-specific modification of peptides and proteins has actually wide programs in probing and perturbing biological systems. Herein we report that 1,2-aminothiol can respond rapidly, particularly and effortlessly with 2-((alkylthio)(aryl)methylene)malononitrile (TAMM) under biocompatible circumstances. This effect goes through a unique mechanism involving thiol-vinyl sulfide exchange, cyclization, and reduction of dicyanomethanide to make 2-aryl-4,5-dihydrothiazole (AD