Ru 介导的 N-芳基硫脲制备苯并噻唑的计算研究:阐明反应机理和不同底物反应活性的起源

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL International Journal of Quantum Chemistry Pub Date : 2024-09-24 DOI:10.1002/qua.27480
Pacharaporn Krawmanee, M. Paul Gleeson, Duangkamol Gleeson
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引用次数: 0

摘要

通过分子内 CS 键形成反应合成新型苯并噻唑的研究日益增多,因为在多种天然产品和药物中都发现了苯并噻唑。Sharma 等人报道了由 N-芳基硫脲前体在钌催化下制备新型苯并噻唑衍生物的方法,并观察到了一系列的反应产率和选择性。我们采用基于密度泛函理论的计算模型来研究生成苯并噻唑产物的反应机理,并帮助揭示不同实验产率和底物特异性的原因。我们提出了一个改进的机理方案,其中决定反应速率的步骤是氧化剂过氧键的同步断裂,以及与此同时来自卤代脲和 Ru 结合水分子的质子耦合电子转移,而不是亲电 RuC 键的活化。证明这是速率决定步骤的证据是:(a) 障碍与缺乏与正交 H 原子相关的动力学同位素效应相一致;(b) 10 种 N-芳基硫脲底物的计算速率决定障碍与观察到的产率有很好的相关性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Computational Investigation of the Ru-Mediated Preparation of Benzothiazoles From N-Arylthioureas: Elucidation of the Reaction Mechanism and the Origin of Differing Substrate Reactivity

Synthesis of novel benzothiazoles via intramolecular CS bond formation reactions is increasingly being explored since they have been found in a wide range of natural products and pharmaceutical agents. Sharma et al. reported the ruthenium-catalyzed preparation of novel benzothiazole derivatives from N-arylthiourea precursors, with a range of reaction yields and selectivity being observed. We have employed a density functional theory-based computational model to investigate the reaction mechanism leading to the benzothiazole product and help uncover the origin of the differing experimental yields and substrate specificities. We proposed a modified mechanistic scheme where the rate-determining step to be the synchronized breaking of the peroxide bond of the oxidizing agent with the concomitant proton-coupled electron transfer from the haloarene urea and a Ru-bound water molecule, not electrophilic RuC bond activation. Evidence for this being the rate-determining step is (a) the barrier is consistent with a lack of kinetic isotope effects associated with the ortho-H atom and (b) the computed rate-determining barriers for 10 N-arylthiourea substrates show good correlation with the observed yield.

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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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