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Here, we report the selective C(sp3)-C(sp3) cleavage/alkynylation of cycloalkylamides for the aminoalkyne synthesis under mild photoredox catalysis conditions. γ- and δ-Aminoalkynes with versatile alkyne and amine substituents are efficiently constructed from cyclopropylamides and cyclobutylamides via amidyl radicals enabled by hypervalent iodine(III) reagents. The catalytic amount of cyclic iodine(III) BI’-OAc facilitated the single-electron oxidation and ring-opening alkynylation of cycloalkylamides, which were investigated by a series of mechanistic probing experiments. Various α-amino substitutions from the oxygen, sulfur, or carbon nucleophile trapping can be performed in gram scale, and the aminoalkyne products easily derivatize to indolizidines, presenting in versatile bioactive fused azacycles.
Liu et al. (Tue,) studied this question.