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Organocatalytic asymmetric [2 + 2] cycloaddition of alkynes with quinones

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Abstract

A chiral phosphoric acid catalyzed enantioselective [2 + 2] cycloaddition of alkynylindols or alkynylnaphthols with quinones is disclosed. A class of functionalized cyclobutenes with excellent yields, diastereo- and enantioselectivities were prepared under mild reaction conditions (70 examples, up to 99% yield, 99% ee, all > 50:1 dr). Mechanistic studies revealed that a dearomatization of indole or naphthol occurred to initiate the cycloaddition, followed by an intramolecular Michael addition with in situ generated allene-iminium or vinylidene-quinone methide intermediate. The competitive [2 + 3] cycloaddition was prevented in this catalytic system. An interesting central to axial chirality conversion via a rearrangement process was realized during transformation of the product.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC 21672170), the Natural Science Basic Research Plan in Shaanxi Province of China (2021JZ-40), and Shaanxi Fundamental Science Research Project for Chemistry & Biology (22JHQ007). The calculations were performed at Chemical HPC Center of NWU.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi’an, 710127, China

    Huai-Ri Sun, Lan Yang, Yu Li, Le Yu, Bo-Bo Gou, Atif Sharif, Qing-Song Jian, Jie Chen & Ling Zhou

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  1. Huai-Ri Sun
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  2. Lan Yang
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  3. Yu Li
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  4. Le Yu
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Correspondence to Jie Chen or Ling Zhou.

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The supporting information is available online at chem.scichina.com and 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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Sun, HR., Yang, L., Li, Y. et al. Organocatalytic asymmetric [2 + 2] cycloaddition of alkynes with quinones. Sci. China Chem. 66, 2292–2299 (2023). https://doi.org/10.1007/s11426-023-1658-9

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