Lewis Acid Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic N-Sulfonylaziridines
Lewis Acid Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic N-Sulfonylaziridines
复制标题
路易斯酸催化外消旋 N-磺酰基氮丙啶的动态不对称转化
DOI：
10.1021/jacs.8b10217
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发表时间：
2018
影响因子：
15
通讯作者：
Chai Zhuo
中科院分区：
文献类型：
--
作者：
Yang Pei-Jun;Qi Ling;Liu Zhen;Yang Gaosheng;Chai Zhuo
本文首次报道了路易斯酸催化的2-（杂）芳基- n -磺酰基叠胺与亲核试剂裂解C-N键的立体会聚转化。这包括与（杂）芳醛和1,3-二取代吲哚的[3 + 2]环反应，与富电子（杂）芳烃的不对称Friedel-Crafts型反应，以及与胺的不对称氨解反应，这些反应可以方便地获得手性1,3-异恶唑烷、吡咯吲哚、2-（杂）芳基苯乙胺和邻二胺。该方法具有Cu(I) -手性BINAP催化剂配合物简单、价格便宜、产率高、非映体和对映体选择性高、反应条件温和等特点。在对照实验的基础上，提出了外消旋叠氮嘧啶的I型动力学不对称转化机理。
The first Lewis acid catalyzed stereoconvergent transformation of racemic 2-(hetero)aryl-N-sulfonylaziridines via C–N bond cleavage with nucleophiles is presented. This includes the [3 + 2] annulations with (hetero)aromatic aldehydes and 1,3-disubstituted indoles, asymmetric Friedel–Crafts type reaction with electron-rich (hetero)arenes, and asymmetric aminolysis with amines, providing facile access to chiral 1,3-isoxazolidines, pyrroloindolines, 2-(hetero)arylphenethylamines, and vicinal diamines. This method features a simple and cheaply available complex of Cu(I)–chiral BINAP catalyst, excellent yield and high diastereo- and enantioselectivities, and mild reaction conditions. A mechanism involving type I dynamic kinetic asymmetric transformations (DyKATs) of the racemic aziridines is proposed based on the results of control experiments.