Oxidative Hetero-Coupling: Iron and Copper-Mediated 1,2Dicarbofunctionalization

Novel strategies, including cross-electrophile coupling and its extension; 1,2-dicarbofunctionalization of alkenes, utilize two distinct electrophiles to generate intricate aliphatic architectures. The redox-neutral 1,2-dicarbofunctionalization is equally effective, utilizing both a nucleophile and an electrophile. These strategies utilize alkyl halides via single-electron transfer (SET) to generate open-shell radicals, alongside the utilization of C(sp2) reagents that adhere to closed-shell two-electron mechanisms. The oxidative hetero 1,2-dicarbofunctionalization of alkenes, utilizing two different nucleophiles, is unprece-dented despite its potential to generate two C(sp3) centers in a single step. This is mostly due to the formation of several byproducts, including the homo-coupling of oxidatively generated alkyl radicals. Here, we demonstrate the hetero-coupling of two distinct nucleophiles by applying the concept of the persistent radical effect (PRE). The approach utilizes unprotected alkyl-carboxylic acids to produce two successive Csp3 centers, including quaternary centers. Studies involving radical trap-ping, binding energy, and DFT corroborate the hypothesized mechanism.