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Copper-catalyzed asymmetric dearomatizing amination of 2-naphthols: Csp2–N coupling via 1,3-reductive elimination

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Abstract

An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I) complex as a chiral catalyst was presented. A variety of optically active β-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions. Mechanistic studies indicated that this Csp2–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-CuIII-amino intermediate in five-membered ring transition states. The origin of enantioselectivity has also been elucidated based on density functional theory calculations.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22188101) and Sichuan Science and Technology Program (2021YJ0561). We appreciate Dr. Bo Gao from the Analytical & Testing Center of Sichuan University for help with LC-MS characterization. We thank Dr. Yuqiao Zhou (Sichuan University) for assistance in X-ray analysis and Dr. Hanjiao Chen (Sichuan University) for assistance with EPR measurement and simulation.

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Authors and Affiliations

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

    Aying Yihuo, Mao** Pu, Zheng Tan, Jibang Liao, Jiuqi Tan, **aohua Liu & **aoming Feng

  2. Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tian**, 300071, China

    Qi-Lin Zhou

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  1. Aying Yihuo
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  2. Mao** Pu
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  3. Zheng Tan
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  7. **aohua Liu
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Correspondence to **aohua Liu or **aoming Feng.

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Supporting information The supporting information is available online at http://chem.scichina.com and http://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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Yihuo, A., Pu, M., Tan, Z. et al. Copper-catalyzed asymmetric dearomatizing amination of 2-naphthols: Csp2–N coupling via 1,3-reductive elimination. Sci. China Chem. (2024). https://doi.org/10.1007/s11426-024-2030-3

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