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Mechanism and origins of gold-catalyzed domino cyclization to spiroindolines: the role of periplanar cooperation and hydrogen bonding interactions
Organic Chemistry Frontiers ( IF 5.4 ) Pub Date : 2020-05-27 , DOI: 10.1039/d0qo00359j
Yunhe Li 1, 2, 3, 4, 5 , Xiang Zhao 1, 2, 3, 4, 5
Affiliation  

The detailed mechanism and origins of gold-catalyzed domino cyclization to indoloazocines by density functional theory are systematically studied. The energy profiles for [Au(PMe3)]+ and [Au(PMe3)SbF6] were investigated. Specifically, the gold-counterion dual catalysis mechanism was the most plausible mechanism for domino cyclization to spiroindolines because of its periplanar cooperation, small activation energy, and hydrogen bonding interactions in the transition states (TS) and intermediates. Based on the Curtin–Hammett principle, the calculated activation energy of 21.0 kcal mol−1 was the rate-determining step for the overall reaction. Besides, the energy profiles for three different models, i.e. catalysts with OTfcounterion, BF4 counterion, and THF solvent, were investigated to confirm the role of hydrogen bonding interactions in the cooperative dual catalysis mechanism. Thus, the obtained theoretical results not only well rationalize the experimental results but also provide insights into the details of the domino cyclization.

中文翻译:

金催化多米诺环化成螺二吲哚的机理和起源:平面内合作和氢键相互作用的作用

利用密度泛函理论系统研究了金催化多米诺环化吲哚并偶氮的详细机理和起源。研究了[Au(PMe 3)] +和[Au(PMe 3)SbF 6 ]的能量分布。具体而言,金-抗衡双重催化机制是多米诺环化成螺二吲哚最合理的机制,因为它具有平面共面作用,小的活化能以及过渡态(TS)和中间体中的氢键相互作用。根据Curtin–Hammett原理,计算得出的21.0 kcal mol -1的活化能是整个反应的速率决定步骤。此外,三种不同模型的能量分布催化剂与光学传递函数-的抗衡离子,BF 4 -的抗衡离子,和THF溶剂,进行了研究,以确认的氢键相互作用在合作双重催化机制中的作用。因此,获得的理论结果不仅使实验结果合理化,而且为深入了解多米诺环化反应提供了见识。
更新日期:2020-06-30
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