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Visible-light-driven thio-carboxylation of alkynes with CO2: facile synthesis of thiochromones

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Abstract

Difunctionalizing carboxylation of alkynes with CO2 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 CO2, which is a visible-light-driven and transition metal-free process. In contrast to previous carboxylations of alkynes via two-electron activation of CO2, mechanistic and computational investigations suggest that the single-electron activation of CO2 is involved in the thio-carboxylation, rendering unique β-carboxylation. The following cyclizing acylation affords important thiochromones efficiently. Moreover, the one-pot method features mild reaction conditions (room temperature, 1 atmosphere of CO2), high chemo- and regio-selectivity, easy scalability and facile derivatization of products to bioactive compounds.

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Acknowledgements

This work was 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) and the Fundamental Research Funds for the Central Universities. We also thank Xiaoyan Wang from the Analysis and Testing Center of Sichuan University as well as Jing Li, Qin-Fang Zhang and Dongyan Deng from the College of Chemistry at Sichuan University for compound testing.

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Authors and Affiliations

  1. Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China

    Meng Miao, Hong Zhao, Lei Song, Si-Shun Yan, Jian-Heng Ye & Da-Gang Yu

  2. College of Pharmacy, Third Military Medical University, Chongqing, 400038, China

    Lei Zhu

  3. School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing, 400030, China

    Lei Zhu, Li-Li Liao & Yu Lan

  4. College of Chemistry and Institute of Green Catalysis, Zhengzhou University, Zhengzhou, 450001, China

    Yu Lan

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  1. Meng Miao
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Correspondence to Jian-Heng Ye, Yu Lan or Da-Gang Yu.

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The authors declare the following competing financial interest(s): A Chinese Patent on this work has been applied with the number 202210655518.3.

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Miao, M., Zhu, L., Zhao, H. et al. Visible-light-driven thio-carboxylation of alkynes with CO2: facile synthesis of thiochromones. Sci. China Chem. 66, 1457–1466 (2023). https://doi.org/10.1007/s11426-022-1554-x

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