Mechanistic insight into the rhodium(III)‐catalyzed ortho‐selective coupling of diverse arenes with 4‐acyl‐1‐sulfonyltriazoles: A computational study,International Journal of Quantum Chemistry

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Mechanistic insight into the rhodium(III)‐catalyzed ortho‐selective coupling of diverse arenes with 4‐acyl‐1‐sulfonyltriazoles: A computational study
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2019-11-26 , DOI: 10.1002/qua.26119
Weirong Wu _{1,

2} , Yue Liu ₁ , Jiayi Hu ₁ , Jiageng Xiong ₁ , Hua Hou ₁

Affiliation

A mechanistic study of the Cp*Rh(III)‐catalyzed annulative coupling of benzimidates with 4‐acyl‐1‐sulfonyltriazoles by CH activation was performed using density functional M06 method. It was demonstrated that the active catalyst during the coupling process should be the cation [Cp*Rh(OAc)]⁺ rather than the neutral Cp*Rh(OAc)₂ and Zn(OAc)₂ as proposed previously by the experimenters. A novel energetically feasible reaction pathway has been revealed theoretically in details. The acetic acid‐mediated cyclization process was confirmed to be the rate‐limiting step with an overall barrier of 24.3 kcal/mol, excluding any importance of the CH cleavage mechanism as supported by the kinetic isotope effect experiments. The major factors responsible for the preferred regioselectivity of N‐pyrimidinylinoles with 4‐acetyl‐1‐sulfonyltriazoles were discussed.

中文翻译：

机械洞察铑（III）催化不同芳烃与4-酰基-1-磺酰基三唑的邻位选择性偶联：计算研究

使用密度泛函M06法对Cp * Rh（III）催化苯甲二酸酯与4-酰基-1-磺酰基三唑的CH活化的环状偶联进行了机理研究。结果表明，偶联过程中的活性催化剂应为阳离子[Cp * Rh（OAc）] ^+，而不是实验人员先前提出的中性Cp * Rh（OAc）₂和Zn（OAc）₂。理论上已经详细揭示了一种新的在能量上可行的反应途径。乙酸介导的环化方法被证实是限速步骤24.3千卡/摩尔的整体屏障，不包括作为C任何重要性H裂解机理受到动力学同位素效应实验的支持。讨论了影响N-嘧啶与4-乙酰基-1-磺酰基三唑的优选区域选择性的主要因素。

更新日期：2019-12-21

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