A computational study to unravel the selectivity in an iron-catalysed [3+2] cycloaddition of aziridine and heterocumulenes

Adhikari Debashis

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A computational study to unravel the selectivity in an iron-catalysed [3+2] cycloaddition of aziridine and heterocumulenes

机译：计算研究以揭示在铁催化的氮丙啶和杂枯烯的[3 + 2]环加成反应中的选择性

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The reaction mechanism of cycloaddition between phenyl aziridine and heterocumulene catalysed by iron salts in water has been modeled computationally to trace the origin of the excellent regioselectivity toward 5-substituted product formation. The calculations reveal that the Lewis-acidic iron centre activates and increases the electrophilicity of the heterocumulene upon binding, so that a nucleophilic aziridine-attack can be invoked. The preferential opening of the substituted C-2-N bond in the following intermediate, dictated by the stability of an incipient carbocation is the key for such selectivity. Since the aziridine ring-opening step is asynchronous, concerted in nature, the iminoazoselenolidine ring retains the stereopurity at the chiral carbon.

机译：通过计算机模拟了水中铁盐催化的苯基氮丙啶和杂异丙苯之间环加成反应的反应机理，以追踪向5取代产物形成的区域选择性极好的起源。该计算表明，路易斯酸性铁中心在结合时活化并增加了杂异丙基苯的亲电性，从而可以引起亲核性氮丙啶攻击。取决于初始碳阳离子的稳定性，在随后的中间体中取代的C-2-N键的优先打开是这种选择性的关键。由于氮丙啶开环步骤是异步的，本质上是一致的，因此亚氨基氮杂亚硒啉环在手性碳上保留了立体纯度。

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《RSC Advances》 |2015年第115期|共6页
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Adhikari Debashis;
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1. A computational study to unravel the selectivity in an iron-catalysed [3+2] cycloaddition of aziridine and heterocumulenes [J] . Adhikari Debashis RSC Advances . 2015,第115期

机译：计算研究以揭示在铁催化的氮丙啶和杂枯烯的[3 + 2]环加成反应中的选择性
2. Unravelling the mechanism and the origin of the selectivity of the [3+2] cycloaddition reaction between electrophilic nitrone and nucleophilic alkene [J] . Chafaa Fouad, Nacereddine Abdelmalek Khorief, Djerourou Abdelhafid Theoretical chemistry accounts . 2019,第12期

机译：解开电泳亚硝酮和亲核烯烃之间[3 + 2]环加入反应的机制和起源的起源
3. Studies on the Formal [3+2] Cycloaddition of Aziridines with Alkenes for the Synthesis of 1-Azaspiroalkanes [J] . Martinand-Lurin Elodie, Gruber Raymond, Retailleau Pascal, The Journal of Organic Chemistry . 2015,第3期

机译：氮丙啶与烯烃的形式[3 + 2]环加成反应合成1-氮杂螺烷的研究
4. Structural diversification of chiral compounds containing adjacentstereocenters based on the catalytic 3+2 cycloaddition of Ccyanonitrones [C] . Tetsuya Ezawa, Yoshihiro Sohtome, MaiAkakabe 日本化学会春季年会 . 2020

机译：基于催化的相邻封闭剂的手性化合物的结构多样化3 + 2环加成Ccyanonitone的环加成
5. Unraveling [3+2] Cycloaddition Reactions Through the Molecular Electron Density Theory [D] . Gutiérrez, Mar Ríos. 2018

机译：通过分子电子密度理论解开[3 + 2]环加成反应
6. A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in 3+2 Cycloaddition Reactions [O] . Luis R. Domingo, Mar Ríos-Gutiérrez 2017

机译：偶氮甲亚胺在3 + 2环加成反应中反应性的分子电子密度理论研究
7. Stereoselective Lewis Acid Mediated (3+2) Cycloadditions of N-H- and N-Sulfonylaziridines with Heterocumulenes [O] . Craig Robert A. II, OConnor Nicholas R., Goldberg Alexander F. G., 2014

机译：立体选择性路易斯酸介导的N-H-和N-磺酰基氮丙啶与异枯烯的（3 + 2）环加成反应

A computational study to unravel the selectivity in an iron-catalysed [3+2] cycloaddition of aziridine and heterocumulenes

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