Herein, a highly exothermic primary amine–polyvalent iodine reaction has been used successfully for selective functionalization of acidic C(sp³)–H groups for a dehydrogenative C–H imination reaction by 4H elimination. Overall, C(sp³)–H imination at 1,5 distances was readily done via organocatalysis using PhI (10 mol%)–mCPBA under ambient conditions.