Metallaphotoredox-catalyzed alkynylcarboxylation of alkenes with CO2 and alkynes for expedient access to β-alkynyl acids
Jincheng Xu, Jun‐Ping Yue, Min Pan, Yichi Chen, Wei Wang, Xi Zhou, Wei Zhang, Jian‐Heng Ye, Da‐Gang Yu
Abstract
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.