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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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