Computations on Pericyclic Reactions Reveal the Richness of Ambimodal Transition States and Pericyclases,Israel Journal of Chemistry

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Computations on Pericyclic Reactions Reveal the Richness of Ambimodal Transition States and Pericyclases
Israel Journal of Chemistry ( IF 2.3 ) Pub Date : 2021-09-02 , DOI: 10.1002/ijch.202100071
K. N. Houk ₁ , Xiao‐Song Xue ₂ , Fang Liu ₃ , Yu Chen ₄ , Xiangyang Chen ₁ , Cooper Jamieson ₁

Affiliation

The pericyclic reaction concept was developed by Woodward and Hoffmann 56 years ago, before accurate quantum mechanical calculations of organic reaction pathways were possible. Since then, computational methods such as density functional theory and coupled-cluster methods have been formulated, and computer speeds have increased a hundred trillion (10¹¹)-fold. The subtleties and timings of bond formation in reactions have been established by high-accuracy quantum mechanical calculations. The field of pericyclic reactions has been enriched by understanding of the borderline between concerted pericyclic reactions and stepwise reactions. Higher-order pericyclic reactions, involving more than six electrons, have ambimodal transition states that can form two, three, or even four products. In addition, while only imagined in the last century, the fact that enzymes can catalyze many pericyclic reactions has been repeatedly established in the 21^st century, aided enormously by computational studies.

中文翻译：

对周环反应的计算揭示了双峰过渡态和环环酶的丰富性

周环反应概念是伍德沃德和霍夫曼在 56 年前提出的，当时有机反应路径的精确量子力学计算成为可能。此后，密度泛函理论、耦合聚类方法等计算方法相继形成，计算机速度提升了百万亿（10 ¹¹）-折叠。反应中键形成的微妙之处和时间已通过高精度量子力学计算确定。通过了解协同周环反应和逐步反应之间的界限，丰富了周环反应领域。涉及六个以上电子的高阶周环反应具有可以形成两个、三个甚至四个产物的双峰过渡态。此外，虽然在上个世纪还只是想象，但酶可以催化许多周环反应的事实在 21 世纪得到了反复证实，这在^计算研究的大力支持下得到了极大的帮助。

更新日期：2021-09-02

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