Phong Dam, Kosala N. Amarasinghe, Chenyang Wang, Olga S. Bokareva, Luis Miguel Azofra, Osama El‐Sepelgy
High Resolution Image Download MS PowerPoint Slide Herein, we report a cobalt-catalyzed method for γ-selective C–H functionalization of aliphatic alcohols via a hydrogen atom transfer (HAT)-based radical relay. This strategy employs a readily available cobalt-salen catalyst under mild conditions, enabling diverse γ-C–H functionalization with excellent site-selectivity. Mechanistic insights were gained through spectroscopic experiments and DFT calculations, confirming the formation of carbon-centered radicals as key intermediates in the reaction pathway. This study offers a powerful tool for site-selective derivatization of alcohols and contributes to the development of sustainable and modular C–H functionalization strategies.