Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp<sup>3</sup>)–H Bonds and Aliphatic Carboxylic Acids
Runze Mao, Srikrishna Bera, Aurélya Christelle Turla, Xile Hu
Abstract
Intermolecular functionalization of C(sp3)–H bonds and aliphatic carboxylic acids enables the efficient synthesis of high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these methods either work for only activated C(sp3)–H bonds or bring in a narrow set of functional groups. Here we describe a Cu-catalyzed process for the diverse functionalization of both unactivated C(sp3)–H bonds and aliphatic carboxylic acids. The process is enabled by the trapping of alkyl radicals generated through hydrogen atom abstraction by arylsulfonyl-based SOMO-philes, which introduces a large array of C, N, S, Se, and halide-based functional groups. The chemoselectivity can be switched from C–H functionalization to decarboxylative functionalization by matching the bond dissociation energy of the hydrogen atom transfer reagent with that of the target C–H or O–H bond.