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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Catalytic metal-free intramolecular hydroaminations of non-activated aminoalkenes: A computational exploration
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Catalytic metal-free intramolecular hydroaminations of non-activated aminoalkenes: A computational exploration

机译：非活化氨基烯烃的无催化金属分子内氢胺化：计算探索

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Frustrated Lewis pairs (FLPs) has been applied to catalytic metal-free hydrogenation. Can the FLP reactivity be used for catalytic hydroamination? Using density functional theory (DFT) calculations, we have explored whether the molecules cat1-cat3, which were previously designed by integrating the dearomatization-aromatization effect and the FLP reactivity, can catalyze the intramolecular hydroaminations of non-activated aminoalkenes to afford nitrogen heterocycles. The study shows that the γ-aminoalkene (am1) hydroamination catalyzed by cat1 proceeds via two steps (aminoalkene N-H bond activation and C-N bond formation) with experimentally accessible energetics, giving the five-membered nitrogen heterocycle product 1,1-dimethylpyrrolidine. The N-H bond activation is reversible. The C-N bond formation step undergoes a concerted mechanism and complies with the Markovnikov addition rule. Possible side reactions which may cause catalyst deactivation were confirmed to be energetically unfavorable. The molecules cat2 and cat3 are less effective than cat1 in catalyzing the am1 hydroamination, but the barriers are not too high. By following the most favorable pathway of the cat1-mediated am1 hydroamination, we further extended the substrate (am1) to other aminoalkenes, including the methyl and phenyl β-substituted am1 (i.e.am2 and am3, respectively), the benzyl-protected primary aminoalkene (am4), and the δ-aminoalkene (am5). The hydroaminations of am2 and am3 have energetics comparable with am1 hydroamination, the am5 hydroamination is energetically less favorable, and the am4 hydroamination is least favorable but could be realizable by elevating the temperature and pressure. We call experimental efforts to synthesize cat1-cat3 or similar new molecules on the basis of the design strategy. This journal is
机译：沮丧的路易斯对（FLP）已应用于无催化金属的加氢反应。 FLP反应性可以用于催化加氢胺化吗？使用密度泛函理论（DFT）计算，我们已经探索了先前通过整合脱芳香化-芳香化作用和FLP反应性设计的分子cat1-cat3是否可以催化未活化的氨基烯烃的分子内加氢胺化反应以提供氮杂环。研究表明，cat1催化的γ-氨基烯烃（am1）加氢胺化反应通过两个步骤（氨基烯烃N-H键激活和C-N键形成）与可实验获得的能量进行，得到了五元氮杂环产物1,1-二甲基吡咯烷。 N-H键激活是可逆的。 C-N键形成步骤经历了协调的机制并且符合马尔可夫尼可夫加法则。已证实可能导致催化剂失活的可能的副反应在能量上不利。 cat2和cat3分子在催化am1加氢胺化方面不如cat1高效，但势垒不太高。通过遵循cat1介导的am1加氢胺化的最有利途径，我们进一步将底物（am1）扩展至其他氨基烯烃，包括甲基和苯基β取代的am1（分别为am2和am3），苄基保护的伯氨基烯烃（am4）和δ-氨基烯烃（am5）。 am2和am3的胺化反应具有与am1胺化反应相当的能量，而am5胺化反应在能量上不利，而am4胺化反应则较差，但可以通过升高温度和压力来实现。我们称根据设计策略来合成cat1-cat3或类似新分子的实验工作。这本日记是

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