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

Abstract 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(sp 3 )−H functionalization. Herein we describe a novel radical alkynylation and allylation of unactivated C(sp 3 )−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(sp 3 )−H functionalization using easily available aliphatic alcohols as feedstock.