Copper-Catalyzed Trifluoromethylation-Initiated Radical 1,2-Aryl Migration in α,α-Diaryl Allylic Alcohols†
Xiaowu Liu
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
Search for more papers by this authorFei Xiong
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
Search for more papers by this authorXuanping Huang
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
Search for more papers by this authorLiang Xu
Center for Organic Chemistry, Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, 710054 (China)
Search for more papers by this authorCorresponding Author
Prof. Dr. 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)
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)
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiaoxing Wu
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)
Search for more papers by this authorXiaowu Liu
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
Search for more papers by this authorFei Xiong
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
Search for more papers by this authorXuanping Huang
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, 190 Kaiyuan Avenue, Guangzhou 510530 (China)
Search for more papers by this authorLiang Xu
Center for Organic Chemistry, Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, 710054 (China)
Search for more papers by this authorCorresponding Author
Prof. Dr. 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)
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)
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiaoxing Wu
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)
Search for more papers by this authorWe 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).
Graphical Abstract
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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