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Specific cross-dimerization of terminal alkynes via Pd/TMEDA catalysis

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Abstract

The cross-dimerization of terminal alkynes is the most straightforward and attractive approach to differently substituted 1,3-enynes, which are vital structural motifs in natural products, biologically active compounds, and organic functional materials, etc. However, due to the inherent issues of the stereo-, regio-, and chemoselectivity, the strategy is less explored and remains problematic in substrate scope, selectivity, and screening of catalytic system, etc. Herein, a specific cross-dimerization of terminal alkynes is developed under Pd/TMEDA catalysis, which produces a series of gem-1,3-enynes (58 examples) in totally moderate to high yields with outstanding functional group tolerance. A cyclopalladium compound might be the key imtermediate, which performs anti-addition-carbometallation, and leads to the exclusive cross-selectivity. The unprecedented features of the reaction, such as anti-addition-carbometallation, easy control of selectivity, wide range of the donor alkynes, and very simple catalytic conditions, allow it not only a facile and functionally diverse synthesis of 1,3-enynes, but also a substantial progress for the textbook reaction.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21878072, 21706058, 22102062, 21725602), the Hunan Provincial Natural Science Foundation of China (2020JJ2011) and the China Postdoctoral Science Foundation (2019M662774).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China

    Lixin Liu, Jianyu Dong, Zuqi Fu, Lebin Su, Shaofeng Wu, Qian Shang, Shuang-Feng Yin & Yongbo Zhou

  2. School of Physics and Chemistry, Hunan First Normal University, Changsha, 410205, China

    Lixin Liu, Jianyu Dong & Lebin Su

  3. School of Chemistry and Materials Engineering, Huizhou University, Huizhou, 516001, China

    Lixin Liu

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  1. Lixin Liu
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  4. Lebin Su
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Correspondence to Jianyu Dong or Yongbo Zhou.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors

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Liu, L., Dong, J., Fu, Z. et al. Specific cross-dimerization of terminal alkynes via Pd/TMEDA catalysis. Sci. China Chem. 65, 2487–2493 (2022). https://doi.org/10.1007/s11426-022-1388-5

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  • DOI: https://doi.org/10.1007/s11426-022-1388-5

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