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

Novel strategies, including cross-electrophile coupling and its extension, 1,2-dicarbofunctionalization of alkenes, utilize two distinct electrophiles to generate intricate aliphatic architectures. Redox-neutral 1,2-dicarbofunctionalization is equally effective. Oxidative hetero-1,2-dicarbofunctionalization of alkenes, utilizing two different nucleophiles, is unprecedented, despite its potential to generate two C(sp³) centers in a single step. This constraint is mostly due to the formation of several byproducts, including the homocoupling of oxidatively generated alkyl radicals. The direct use of abundant natural functional groups, such as carboxylic acids, in organic synthesis is particularly appealing. Nonetheless, they are utilized in 1,2-dicarbofunctionalization in the form of redox-active esters alongside other coupling partners. Here, we demonstrate the heterocoupling of two distinct nucleophiles by applying the concept of the persistent radical effect. The approach utilizes unprotected alkyl carboxylic acids to produce two successive C(sp³) centers, including quaternary centers. Studies involving radical trapping, binding energy, and DFT calculations corroborate the hypothesized mechanism.