摘要
Difunctionalizing carboxylation of alkynes with CO_(2)is a sustainable and important strategy to generate valuable acrylate derivatives from both readily available starting materials.Such protocols,however,always suffer from the use of excess metallic reagents and transition metal residue.Herein,we report the first thio-carboxylation of alkynes with thiophenols and CO_(2),which is a visible-light-driven and transition metal-free process.In contrast to previous carboxylations of alkynes via two-electron activation of CO_(2),mechanistic and computational investigations suggest that the single-electron activation of CO_(2)is involved in the thio-carboxylation,rendering uniqueβ-carboxylation.The following cyclizing acylation affords important thiochromones efficiently.Moreover,the one-pot method features mild reaction conditions(room temperature,1 atmosphere of CO_(2)),high chemo-and regio-selectivity,easy scalability and facile derivatization of products to bioactive compounds.
基金
supported by the National Natural Science Foundation of China(22225106,21822108,21822303)
the Sichuan Science and Technology Program(20CXTD0112)
the Central Government Funds of Guiding Local Scientific and Technological Development for Sichuan Province(2021ZYD0063)
the Fundamental Research Funds from Sichuan University(2020SCUNL102)
the Fundamental Research Funds for the Central Universities。