Cobalt-Catalyzed Selective Cross-Addition of Two Similar Acrylates for the Synthesis of Adipates and Glutarates

Adipic acids and glutaric acids are core intermediates in polymer production. However, neither industry nor laboratory synthesis enables facile access to main-chain substituted diacid derivatives, restricting the development of novel monomers for polymerization. Herein, we report a regiodivergent synthesis of substituted adipates and glutarates from two acrylates with minimal structural and electronic differences on a multigram scale with recyclable cobaloxime. Chemoselectivity of cross-coupling over self-coupling reaches 25:1 and was determined by the interaction mode between cobalt catalyst and different acrylates. Single regioselectivity of cobalt hydride addition toward two specific acrylates could be achieved under basic or neutral reaction conditions. Mechanistic investigations revealed a significant chemoselectivity (ΔΔG‡ > 3.0 kcal mol–1), indicating that substrate-specific local electronic properties govern chemo- and regioselectivity, providing predictive insight into rational selectivity control.