Chinese Journal of Catalysis ›› 2015, Vol. 36 ›› Issue (1): 68-77.DOI: 10.1016/S1872-2067(14)60204-7

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Catalytic asymmetric construction of spiro pyrrolidines with contiguous quaternary centers via 1,3-dipolar cycloaddition of azomethine ylides

Tanglin Liua, Qinghua Lia, Zhaolin Hea, Jiawei Zhanga, Chunjiang Wanga,b   

  1. a College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China;
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 230032, China
  • Received:2014-06-26 Revised:2014-07-22 Online:2014-12-31 Published:2014-12-31
  • Supported by:

    This work was supported by the National Basic Research Program of China (973 Program, 2011CB808600), the National Natural Science Foundation of China (21172176, 21372180), Hubei Province Natural Science Foundation (ZRZ0273), Fundamental Research Funds for the Central Universities, and an Academic Award for Excellent PhD Candidates Funded by the Ministry of Education of China (5052011203011).

Abstract:

Bioactive 5-aza-spiro[2,4]heptanes with high functionality and up to three contiguous all-carbon quaternary stereogenic centers were synthesized by Cu(I)-catalyzed asymmetric endo-selective 1,3-dipolar cycloaddition of azomethine ylides with cyclopropylidene acetates. This synthesis system performs well for a broad scope of substrates. α-unsubstituted/α-substituted azomethine ylides and cyclopropylidene acetates are compatible 1,3-dipoles and dipolarophiles, which afford the spiro heterocycles with contiguous quaternary centers at 2-, 3- and 4-positions of the pyrrolidine ring in good yield (up to 97%) and high diastereoselectivity (95:5->98:2 d.r) and excellent enantioselectivity (87%-98% ee).

Key words: Asymmetric catalysis, Quaternary stereogenic center, 1,3-Dipolar cycloaddition, Azomethine ylide, Cyclopropylidene acetate, 5-Aza-spiro[2,4]heptane