Recent advances in remote C(sp3)–H functionalization via chelating group-assisted metal-catalyzed chain-walking reaction

Aliphatic C(sp3)–H moieties are ubiquitous in numerous organic compounds. Direct functionalization of inert C(sp3)–H bonds is a powerful and straightforward approach for the efficient construction of diverse carbon–carbon or carbon–heteroatom bonds. Chelating group directed metal-catalyzed remote functionalization of readily available alkenes has emerged as an appealing strategy for rapidly accessing various value-added aliphatic molecules. With the aid of directing groups, various α-, β- and γ-functionalized alkanes could be synthesized smoothly with excellent regioselectivity. The preferred formation of a stable five- or six-membered metallacycle intermediate terminates the chain-walking at a specific methylene site, which serves as the driving force for excellent site-selective migratory functionalization. This review herein is aimed at summarizing the recent progress on the metal-catalyzed regiodivergent functionalization of unactivated alkenes by merging alkene isomerization and cross-coupling with the assistance of directing auxiliary. Last but not least, the current situations and future directions in this field are highlighted and discussed.