Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids

作者：Jincheng Xu, Jun‐Ping Yue, Min Pan, Yichi Chen, Wei Wang, Xi Zhou, Wei Zhang, Jian‐Heng Ye, Da‐Gang Yu · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-57060-w · 被引用次数：22 · 研究领域：Carbon dioxide utilization in catalysis、CO2 Reduction Techniques and Catalysts、Asymmetric Hydrogenation and Catalysis

Carboxylation with CO2 offers an attractive and sustainable access to valuable carboxylic acids. Among these methods, direct C−H carboxylation of terminal alkynes with CO2 has attracted much attention for one-carbon homologation of alkynes, enabling rapid synthesis of propiolic acids. In contrast, the multi-carbons homologation of alkynes with CO2 to construct important non-conjugated alkynyl-containing acids has not been reported. Herein, we present alkynylcarboxylation of alkenes with CO2 via photoredox and copper dual catalysis. This protocol provides a direct and practical method to form valuable non-conjugated alkynyl acids from readily available alkynes, alkenes and CO2. Additionally, this approach also features mild (room temperature, 1 atm of CO2) and redox-neutral conditions, high atom and step economy, good functional group tolerance, and high selectivities. Moreover, diverse transformations of the β-alkynyl acid products and the rapid synthesis of bioactive molecule (GPR40/FFA1 agonist) further illustrate the synthetic utility of this methodology. The report for the multi-carbon homologation of alkynes with CO2 to construct important non-conjugated alkynyl-containing acids is rare. Herein, the authors report alkynylcarboxylation of alkenes with CO2 via photoredox and copper dual catalysis, affording non-conjugated alkynyl acids from readily available alkynes, alkenes and CO2.