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

Abstract

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.