Enantioselective Nickel-Electrocatalyzed Reductive Propargylic Carboxylation with CO 2 .

The exploitation of carbon dioxide (CO 2 ) 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 2 fixation, facilitating the formation of C(sp 3 )-C(sp 2 ) 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 2 . The efficacy of this transformation is exemplified by its successful utilization in the asymmetric total synthesis of ( S )-arundic acid, ( R )-PIA, ( S )-chizhine D, ( S )-cochlearin G, and ( S , S )-alexidine, thereby underscoring the potential of asymmetric electrosynthesis to achieve complex molecular architectures sustainably.