On treatment of triazoles having an N-sulfonyl-protected benzylamine moiety with [Rh2(C7H15CO2)4], intramolecular C−H bond insertion takes place at the benzylic position to give cis-N-sulfonyl-2-aryl-3-[(sulfonylimino)methyl]pyrrolidines in good yields and with highly stereoselectivities. Analogously, the similar treatment of triazoles having an ether or even an alkyl moiety affords 2-alkyl- or 2-aryl-3-[(sulfonylimino)methyl]tetrahydrofurans or a 2-alkyl-3-[(sulfonylimino)methyl]cyclopentane in good yields.