The reactions of thiophene- and N-benzylindole-containing gem-acetylnitroethenes with 2-aminobenzothiol lead to the formation of 4-methyl-3-nitro-2,3-dihydro-1,5-benzothiazepines. At the same time, only S-adducts were formed in the reactions of gembenzoylnitroethenes containing a thiophene, furan, or N-benzylindole substituent with 2-aminobenzothiol.