Enantioselective Formation of Cyano‐Bearing All‐Carbon Quaternary Stereocenters: Desymmetrization by Copper‐Catalyzed N‐Arylation |
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| Authors: | Dr. Fengtao Zhou Gui‐Juan Cheng Wenqiang Yang Yan Long Shasha Zhang Prof. Dr. Yun‐Dong Wu Dr. Xinhao Zhang Prof. Dr. Qian Cai |
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| Affiliation: | 1. Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences (GIBH), No.190 Kaiyuan Avenue, Guangzhou Science Park, Guangzhou, 510530 (China);2. Current Address: Molecular Catalyst Research Center, Chubu University, Aichi, 487‐8501 (Japan);3. Lab of Computational Chemistry and Drug Design, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055 (China);4. College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081 (China) |
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| 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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| Keywords: | asymmetric catalysis copper chirality heterocycles synthetic methods |
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