Enantioselective Formation of Cyano-Bearing All-Carbon Quaternary Stereocenters: Desymmetrization by Copper-Catalyzed N-Arylation†
Dr. Fengtao Zhou
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Current Address: Molecular Catalyst Research Center, Chubu University, Aichi, 487-8501 (Japan)
These authors contributed equally to this work.
Search for more papers by this authorGui-Juan Cheng
Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
These authors contributed equally to this work.
Search for more papers by this authorWenqiang Yang
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
These authors contributed equally to this work.
Search for more papers by this authorYan Long
College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081 (China)
Search for more papers by this authorShasha Zhang
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Search for more papers by this authorProf. Dr. Yun-Dong Wu
Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
Search for more papers by this authorCorresponding Author
Dr. Xinhao Zhang
Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
Xinhao Zhang, Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
Qian Cai, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Search for more papers by this authorCorresponding Author
Prof. Dr. Qian Cai
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Xinhao Zhang, Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
Qian Cai, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Search for more papers by this authorDr. Fengtao Zhou
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Current Address: Molecular Catalyst Research Center, Chubu University, Aichi, 487-8501 (Japan)
These authors contributed equally to this work.
Search for more papers by this authorGui-Juan Cheng
Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
These authors contributed equally to this work.
Search for more papers by this authorWenqiang Yang
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
These authors contributed equally to this work.
Search for more papers by this authorYan Long
College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081 (China)
Search for more papers by this authorShasha Zhang
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Search for more papers by this authorProf. Dr. Yun-Dong Wu
Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
Search for more papers by this authorCorresponding Author
Dr. Xinhao Zhang
Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
Xinhao Zhang, Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
Qian Cai, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Search for more papers by this authorCorresponding Author
Prof. Dr. Qian Cai
Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Xinhao Zhang, Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China)
Qian Cai, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China)
Search for more papers by this authorThe authors are grateful to the 100-talent program of CAS, NSFC (21272234, 21133002, & 21232001), the MOST of China (2013CB911501), and the Shenzhen STIC (KQTD201103) for their financial support. We also thank Dr. Jingsong Liu at GIBH for the X-ray experiments.
Abstract
The enantioselective construction of all-carbon quaternary stereocenters is one of the most challenging fields in asymmetric synthesis. An asymmetric desymmetrization strategy offers an indirect and efficient method for the formation of all-carbon stereocenters. An enantioselective formation of cyano-bearing all-carbon quaternary stereocenters in 1,2,3,4,-tetrahydroquinolines and 2,3,4,5-tetrahydro-1H-benzo[b]azepines by copper-catalyzed desymmetric N-arylation is demonstrated. The cyano group at the prochiral center plays a key role for the high enantioselectivity and works as an important functional group for further transformations. DFT studies provide a model which successfully accounts for the origin of enantioselectivity.
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