Copper-Catalyzed Trifluoromethylation-Initiated Radical 1,2-Aryl Migration in α,α-Diaryl Allylic Alcohols

Authors

  • Xiaowu Liu,

    1. Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
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  • Fei Xiong,

    1. Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
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  • Xuanping Huang,

    1. Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
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  • Liang Xu,

    1. Center for Organic Chemistry, Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, 710054 (China)
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  • Prof. Dr. Pengfei Li,

    Corresponding author
    1. Center for Organic Chemistry, Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, 710054 (China)
    • Pengfei Li, Center for Organic Chemistry, Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, 710054 (China)

      Xiaoxing Wu, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)

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  • Prof. Dr. Xiaoxing Wu

    Corresponding author
    1. Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
    • Pengfei Li, Center for Organic Chemistry, Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, 710054 (China)

      Xiaoxing Wu, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)

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  • We are grateful for financial support of this work by a Start-up Grant from Guangzhou Institutes of Biomedicine and Health (GIBH), and by the National Science Foundation of China (grant numbers 21202168 and 21202129).

Abstract

original image

Not only symmetrical, but also unsymmetrical α,α-diaryl allylic alcohols are employed as substrates in the title reaction. A number of arenes and even heteroarenes underwent radical 1,2-aryl migration (“neophyl rearrangement”) to produce α-aryl β-trifluoromethyl ketones. The preferential migration of electron-deficient aryl groups over electron-rich ones in unsymmetrical substrates supports the radical mechanism, which was further confirmed by DFT calculations.

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