Recent advances in alkoxy radical-promoted C–C and C–H bond functionalization starting from free alcohols
Xinxin Wua and Chen Zhu *ab（朱晨）
a Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123, China.
b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
Chem. Commun., 2019, 55, 9747--9756
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.