Enantioselective Nickel-Electrocatalyzed Reductive Propargylic Carboxylation with CO<sub>2</sub>
Qingdong Hu, Boyuan Wei, Mingxu Wang, Minghao Liu, Xiao‐Wang Chen, Chuan‐Kun Ran, Gefei Wang, Ziting Chen, Haoze Li, Jin Song, Da‐Gang Yu, Chang Guo
Abstract
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.