Asymmetric Total Synthesis of Apocynaceae Hydrocarbazole Alkaloids (+)-Deethylibophyllidine and (+)-Limaspermidine

作者:Du Ji Yuan; Zeng Chao; Han Xiao Jie; Qu Hu; Zhao Xian He; An Xian Tao; Fan Chun An
来源:Journal of the American Chemical Society, 2015, 137(12): 4267-4273.
DOI:10.1021/jacs.sb01926

摘要

An unprecedented asymmetric catalytic tandem aminolysis/aza-Michael addition reaction of spirocyclic para-dienoneimides has been designed and developed through organocatalytic enantioselective desymmetrization. A unified strategy based on this key tandem methodology has been divergently explored for the asymmetric total synthesis of two natural Apocynaceae alkaloids, (+)-deethylibophyllidine and (+)-limaspermidine. The present studies not only enrich the tandem reaction design concerning the asymmetric catalytic assembly of a chiral all-carbon quaternary stereocenter contained in the densely functionalized hydrocarbazole synthons but also manifest the potential for the application of the asymmetric catalysis based on the para-dienone chemistry in asymmetric synthesis of natural products.

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