Synthesis of the aziridinomitosene skeleton by intramolecular Michael addition of alpha-lithioaziridines: an aromatic route featuring deuterium as a removable blocking group.
Synthesis of the aziridinomitosene skeleton by intramolecular Michael addition of alpha-lithioaziridines: an aromatic route featuring deuterium as a removable blocking group.
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通过α-锂硫代氮丙啶的分子内迈克尔加成合成氮丙啶基核糖烯骨架：以氘作为可去除的封闭基团的芳香路线。
DOI：
10.1021/jo030223i
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
Little,JeremyD
中科院分区：
文献类型：
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作者：
Vedejs,Edwin;Little,JeremyD
研究了1，2-氮杂环吡咯(1，2-a)吲哚34的聚合合成路线。这条路线的主要特征包括：在从27to30a到30a的锡−锂交换过程中阻止不希望发生的吲哚锂化的动力学同位素效应，分子内的迈克尔加成产生烯醇化31a，以及通过捕捉苯基硒氯而转化为34。34中当时的三苯基的还原裂解允许获得含有氮杂环N-−H亚基的四环氮杂二异三烯。用LAH还原34中的C(9)酯，得到伯醇35，其中C(9)、C(9a)、C(10)的氧化态与氮杂二茂烯相对应，34的去保护得到37。
A convergent synthetic route to the 1,2-aziridinopyrrolo(1,2-a)indole34has been developed. Key features of this route include the deuterium kinetic isotope effect to block undesired indole lithiation during tin−lithium exchange from27ato30a, the intramolecular Michael addition to generate the enolate31a, and conversion into34by trapping with phenylselenenyl chloride. Reductive cleavage of theN-trityl group in34allows access to tetracyclic aziridinomitosenes containing the aziridine N−H subunit. Reduction of the C(9) ester in34with LAH gives the primary alcohol35with the correct C(9), C(9a), C(10) oxidation state corresponding to the aziridinomitosenes, and deprotection of34affords37.