The mechanism of the dirhodium-catalyzed combined C–H functionalization/Cope rearrangement (CH/Cope) reaction discovered by the Davies group has been investigated with density functional theory (DFT) calculations and quasi-classical molecular dynamics (MD) simulations. Computations from the Davies group previously showed that there is a post-transition state bifurcation leading to a direct CH reaction and also to the CH/Cope product. While this work was in preparation, the Tantillo group and the Ess group independently reported quantum mechanical and molecular dynamics studies on the dirhodium-tetracarboxylate-catalyzed diazoester CH/Cope and CH insertion reactions with 1,3-cyclohexadiene and 1,4-cyclohexadiene, respectively. The Tantillo group cited “dynamic mismatching” to explain the origins of the low yield of CH/Cope products in some experiments; the Ess group explained the origins of product selectivity from the perspective of TS vibrational modes and their synchronization that occurs at the entropic intermediates. We report quasi-classical trajectories for the reaction of the carbene with 1-methylcyclohexene that afford both the CH/Cope and C–H insertion products. After passing through the transition state that involves mostly hydrogen transfer, momentum drives the reaction trajectories toward the CH/Cope products.

中文翻译：

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戴维斯双峰 C-H 官能团化/Cope 重排反应的分子动力学


Davies 小组发现的二铕催化的联合 C-H 功能化/Cope 重排 （CH/Cope） 反应的机制已通过密度泛函理论 （DFT） 计算和准经典分子动力学 （MD） 模拟进行了研究。Davies 小组之前的计算表明，存在一个过渡态后分叉，导致直接的 CH 反应以及 CH/Cope 产物。在这项工作准备期间，Tantillo 小组和 Ess 小组分别报告了二锕-四羧酸盐催化的重氮酯 CH/Cope 和 CH 插入反应与 1,3-环己二烯和 1,4-环己二烯的量子力学和分子动力学研究。Tantillo 小组引用了“动态错配”来解释一些实验中 CH/Cope 产物产量低的根源;Ess 小组从 TS 振动模式及其在熵中间体发生的同步的角度解释了产物选择性的起源。我们报道了卡宾与 1-甲基环己烯反应的准经典轨迹，该轨迹同时产生 CH/Cope 和 C-H 插入产物。在通过主要涉及氢转移的过渡态后，动量驱动反应轨迹向 CH/Cope 产物发展。