Recent advances in alkoxy radical-promoted C-C and C-H bond functionalization starting from free alcohols.

Direct functionalization of inert C(sp3)-C(sp3) and C(sp3)-H bonds represents one of the most valuable synthetic tactics, yet large obstacles remain in terms of reactivity and selectivity. Alkoxy radicals enable C-C bond scission via β-C elimination and C(sp3)-H bond cleavage through a hydrogen atom transfer (HAT) process, thus providing an efficient method to address these problems. In view of atom- and step-economy, the direct use of abundant alcohols as alkoxy radical precursors in radical transformations is of high synthetic value. This feature article summarizes our recent achievements in (a) C(sp3)-C(sp3) bond cleavage via ring-opening of cycloalkanols and (b) site-specific C(sp3)-H functionalization of unprotected aliphatic alcohols, along with the reconstruction of various new chemical bonds, e.g. C-halogen, C-C, C-N, C-S, and C-Se bonds.