Enantioselective Nickel-Electrocatalyzed Reductive Propargylic Carboxylation with CO.

The exploitation of carbon dioxide (CO) as a sustainable, plentiful, and harmless C1 source for the catalytic synthesis of enantioenriched carboxylic acids has long been acknowledged as a pivotal task in synthetic chemistry. Herein, we present a current-driven nickel-catalyzed reductive carboxylation reaction with CO fixation, facilitating the formation of C(sp)-C(sp) bonds by circumventing the handling of moisture-sensitive organometallic reagents. This electroreductive protocol serves as a practical platform, paving the way for the synthesis of enantioenriched propargylic carboxylic acids (up to 98% enantiomeric excess) from racemic propargylic carbonates and CO. The efficacy of this transformation is exemplified by its successful utilization in the asymmetric total synthesis of ()-arundic acid, ()-PIA, ()-chizhine D, ()-cochlearin G, and (,)-alexidine, thereby underscoring the potential of asymmetric electrosynthesis to achieve complex molecular architectures sustainably.