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Silicon-mediated enantioselective synthesis of structurally diverse α-amino acid derivatives

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Abstract

The catalytic asymmetric synthesis of novel and chiral amino acid derivatives with unconventional chemo-, diastereo-, and enantio-selectivity remains a paramount challenge. Herein we reported a novel protocol for the use of highly enantioselective copper-catalyzed cycloaddition of α,β-unsaturated acylsilanes as a springboard reaction for the facile synthesis of structurally diversified pyrrolidines and complicated α-amino esters by desilylation. The newly developed process could provide a wide range of synthetically useful acylsilane-substituted pyrrolidines (ASiP) in high yields and excellent diastereo- and enantio-selectivities with Cu/(R)-XylBINAP complex as the catalyst. And the downstream desilylation transformation enables to expand the potntial applications of 1,3-dipolar cycloaddition in the construction of structurally unique amino acid derivatives, in which an unprecedented and concerted fluoride anion-promoted C-X (X=H, Si, N, C) bond cleavage occurred to the enantioselective construction of aldehyde-substituted pyrrolidines, linear cinnamaldehyde or alkene-substituted amino esters in high ee values.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21773051, 21702211, 21703051), Zhejiang Provincial Natural Science Foundation of China (LZ18B020001, LQ19B040001, LY18B020013), and the Hangzhou Science and Technology Bureau of China (20180432B05). The authors thank K.Z. Jiang and X.Q. Xiao for their assistance on the MS and X-ray analysis, the technicians of our group, and the members of our NMR, MS and HPLC departments for their excellent service. L.-W. Xu also thank Prof. X.Q. Hu (Zhejiang University of Technology) and Prof. Y. Lu (National University of Singapore) for their help and discussion in this work.

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Authors and Affiliations

  1. Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, and Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou, 311121, China

    Jun-Han Ma, Li Li, Yu-Li Sun, Zheng Xu, Ke-Fang Yang, Jian Cao, Yu-Ming Cui, Guan-Wu Yin & Li-Wen Xu

  2. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute (SRI) and Lanzhou Institute of Chemical Physics (LICP), University of Chinese Academy of Sciences (UCAS), Lanzhou, 730000, China

    Xing-Feng Bai & Li-Wen Xu

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  1. Jun-Han Ma
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  2. Li Li
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  3. Yu-Li Sun
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Correspondence to Li-Wen Xu.

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Ma, JH., Li, L., Sun, YL. et al. Silicon-mediated enantioselective synthesis of structurally diverse α-amino acid derivatives. Sci. China Chem. 63, 1082–1090 (2020). https://doi.org/10.1007/s11426-020-9768-x

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  • DOI: https://doi.org/10.1007/s11426-020-9768-x

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