Direct Synthesis of Adipic Esters and Adiponitrile via Photoassisted Cobalt‐Catalyzed Alkene Hydrodimerization

The direct hydrodimerization of acrylates and acrylonitrile offers a general streamlined access to industrially important intermediates to nylon 6,6. However, a practical catalytic method for this process has thus far underdeveloped owing to the challenges in regioselectivity and environmental compatibility of applied reagents. Here, we report a cobalt‐catalyzed tail‐to‐tail hydrodimerization of activated alkenes driven by a visible‐light photoredox catalysis at ambient temperature, which is applicable to both adipates and adiponitrile synthesis from potentially renewable feedstocks. This protocol utilizes half equivalent of hantzsch ester as a recyclable two‐electron and two‐proton donor with the assistance of catalytic amount of base as a proton shuttle, and has been shown to be highly regioselective and efficient for hydrodimerizing various activated alkenes to 1,4‐difunctionalized butane derivatives. This work disclosed a visible‐light‐induced cobalt‐catalyzed tail‐to‐tail hydrodimerization of activated alkenes to 1,4‐difunctional butanes, providing a general route to important industrial intermediates to nylon 6,6. This protocol is highly efficient for various activated alkenes at ambient temperature utilizing hantzsch ester as a recyclable two‐electron and two‐proton donor with assistant of catalytic amount of base as the proton shuttle.