Bifunctional thiourea-catalyzed enantioselective double Michael reaction of γ,δ-unsaturated β-ketoester to nitroalkene:: asymmetric synthesis of (-)-epibatidine

被引:159
作者
Hoashi, Y [1 ]
Yabuta, T [1 ]
Takemoto, Y [1 ]
机构
[1] Kyoto Univ, Grad Sch Pharmaceut Sci, Sakyo Ku, Kyoto 6068501, Japan
关键词
thiourea; organocatalyst; Michael reaction; asymmetric synthesis; gamma; delta; -unsaturated beta-ketoester; (-)-epibatidine;
D O I
10.1016/j.tetlet.2004.10.082
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The asymmetric synthesis of 4-nitrocyclohexanone derivatives has been accomplished by enantio selective double Michael additions of gamma,delta-unsaturated beta-ketoesters to nitroalkenes using a catalytic amount of bifunctional thiourea and TMG. The three contiguous stereogenic centers of the obtained products were constructed with good to high diastereoselectivity and up to 92% ee. The biologically active natural product, (-)-epibatidine, has been synthesized from the intermediate 11a in seven steps in 30% overall yield. (C) 2004 Elsevier Ltd. All rights reserved.
引用
收藏
页码:9185 / 9188
页数:4
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