Free Alcohol‐Mediated Radical Alkynylation and Allylation of Unactivated C(sp³)−H Bonds

The daunting challenges in converting alcoholic O-H bonds with high bond-dissociation energy (BDE) to alkoxy radicals and harnessing those unruly reaction species largely limit exploiting free alcohols in C(sp³)-H functionalization. Herein we describe a novel radical alkynylation and allylation of unactivated C(sp³)-H bonds with unmodified aliphatic alcohols. The use of phenyliodine bis(trifluoroacetate) (PIFA) enables the formation of alkoxy radicals under mild photochemical conditions. α-Methyl styrene serves as a sacrificial-reagent that significantly improves the reaction outcomes. This transition-metal free protocol further features broad substrate scope, exclusive site-selectivity, high product diversity, and simple operation, supplying a robust manifold for C(sp³)-H functionalization using easily available aliphatic alcohols as feedstock.