Stereoselective Synthesis of Polycycles Containing an Aziridine Group: Intramolecular aza-Diels-Alder Reactions of Unactivated 2H-Azirines with Unactivated Dienes.

Stereoselective Synthesis of Polycycles Containing an Aziridine Group: Intramolecular aza-Diels-Alder Reactions of Unactivated 2H-Azirines with Unactivated Dienes.
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含有氮丙啶基团的多环的立体选择性合成:未活化的 2H-氮丙啶与未活化的二烯的分子内氮杂-狄尔斯-阿尔德反应

DOI:
10.1002/anie.201510096
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发表时间:
2016-02
期刊:
Angew. Chem., Int. Ed.
影响因子:
--
通讯作者:
Shen, Mei-Hua
Shen, Mei-Hua
中科院分区:
其他
文献类型:
--
作者:
Wu, Hao;Han, Mei;Han, Run-Ze;Shen, Mei-Hua

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带有侧链二烯的乙烯基叠氮可以热分解成相应的氮杂环丙烷中间体,该中间体可以立即用于分子内的氮杂-Diels-桤木反应,以提供具有优异立体选择性的含氮杂环丙烷的反式稠合三环核结构。该方法提供了一个简单的进入复杂的多环碱金属,可以进一步阐述通过开环反应和氮丙啶部分的环膨胀,以及通过烯烃基团的二羟基化。
Vinyl azide with a pendent diene can undergo thermal decomposition to a related azirine intermediate, which was used immediately in an intramolecular aza-Diels-Alder reaction to furnish an aziridine-containing trans-fused tricyclic core structure with excellent stereoselectivity. The method provides a facile entry to complex polycyclic alkaliods which can be further elaborated by ring-opening reactions and ring expansion of the aziridine moiety, as well as by dihydroxylation of the alkene group.
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