González-Navarrete Patricio, Andrés Juan, Safont V Sixte
Departamento de Química Física y Analítica, Universitat Jaume I, 12071, Castelló de la Plana, Spain.
Phys Chem Chem Phys. 2017 Dec 20;20(1):535-541. doi: 10.1039/c7cp07557j.
A comprehensive theoretical investigation of the thermal Claisen rearrangement of allyl vinyl ether (AVE) to allylacetaldehyde has been carried out. We present the use of the electron localization function (ELF) to monitor the bonding evolution aspects in the course of this thermal rearrangement and the results are compared with a photo-impulsive process where instantaneous vibration frequencies are monitored [I. Iwakura, Phys. Chem. Chem. Phys., 2011, 12, 5546-5555]. Our results reveal an asynchronous electron density rearrangement inasmuch that the breaking of the C3-O bond and the formation of C1-C5 do not take place simultaneously. We also demonstrate how the bonding evolution brings about the natural appearance of the curly arrows representing the electronic flow in molecular rearrangements. This holds the key to gaining an unprecedented insight into the mapping of the electron density flow while the bonds change throughout the reaction progress.
对烯丙基乙烯基醚（AVE）热重排为烯丙基乙醛的过程进行了全面的理论研究。我们展示了利用电子定域函数（ELF）来监测该热重排过程中的键合演化情况，并将结果与监测瞬时振动频率的光脉冲过程进行了比较[岩仓一，《物理化学化学物理》，2011年，第12卷，5546 - 5555页]。我们的结果揭示了一种异步的电子密度重排，即C3 - O键的断裂和C1 - C5键的形成并非同时发生。我们还展示了键合演化如何导致在分子重排中代表电子流动的弯箭头自然出现。这是在整个反应进程中键发生变化时，以前所未有的方式深入了解电子密度流映射的关键。
