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Chiral Brønsted acid-catalyzed asymmetric intermolecular [4 + 2] annulation of ynamides with para-quinone methides

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Abstract

Catalytic asymmetric transformations of ynamides have attracted considerable attention in recent years. However, most of them were limited to intramolecular reactions or required metal catalysts. Herein, a chiral Brønsted acid-catalyzed asymmetric intermolecular [4 + 2] annulation of ynamides with para-quinone methides (p-QMs) is disclosed, which not only represents the first metal-free protocol for catalytic asymmetric nucleophilic addition of ynamides to electrophiles, but also constitutes the first enantioselective annulation between p-QMs and alkynes. This methodology leads to the practical synthesis of biologically important chiral 4-aryl-3,4-dihydrocoumarins and 4-aryl-coumarins. Preliminary control experiments indicate that the ortho-hydroxyphenyl substituted p-QMs could isomerize into ortho-quinone methides (o-QMs) in the presence of chiral catalyst, which further react with ynamides via enantioselective [4 + 2] annulation, to generate the chiral product.

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Acknowledgements

This work was supported by the Ministry of Science and Technology (MOST) (2021YFC2100100), the National Natural Science Foundation of China (22125108, 22121001, 92056104), the President Research Funds from **amen University (20720210002), the Natural Science Foundation of Jiangsu Province (BK20211059), the Project of Science and Technology of Xuzhou Government (KC22080), and the National Fund for Fostering Talents of Basic Science (NFFTBS) (J1310024).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory for Chemical Biology of Fujian Province and State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, **amen University, **amen, 361005, China

    Hang-Hao Li, Ya-Nan Meng, Can-Ming Chen, Yu-Qi Wang, Zhi-**n Zhang, Bo Zhou & Long-Wu Ye

  2. Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, Xuzhou, 221004, China

    Zhou Xu

  3. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tian**, 300071, China

    Long-Wu Ye

  4. State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China

    Long-Wu Ye

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  1. Hang-Hao Li
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Correspondence to Zhi-**n Zhang, Zhou Xu or Long-Wu Ye.

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The supporting information is available online at chem.scichina.com and springer.longhoe.net/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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Li, HH., Meng, YN., Chen, CM. et al. Chiral Brønsted acid-catalyzed asymmetric intermolecular [4 + 2] annulation of ynamides with para-quinone methides. Sci. China Chem. 66, 1467–1473 (2023). https://doi.org/10.1007/s11426-022-1536-9

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