Ito Takuma, Harabuchi Yu, Maeda Satoshi
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-8628, Japan.
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
Phys Chem Chem Phys. 2020 Jul 1;22(25):13942-13950. doi: 10.1039/d0cp02379e.
Paths of Diels-Alder reactions between 2-vinylfuran and 3-methoxycarbonylcyclopentadienone were systematically explored by the multicomponent version of the artificial force induced reaction (MC-AFIR) method. In this reaction, the dynamical bifurcation in which a single transition state (TS) relates to two different products has been reported to occur [J. B. Thomas, et al., J. Am. Chem. Soc., 2008, 130, 14544-14555]. In this paper, based on the MC-AFIR method, we propose a procedure to systematically explore so called ambimodal TSs through which the dynamical bifurcation occurs. The present procedure finds candidates of TSs that may cause the dynamical bifurcation from the logs of an automated reaction path search by the MC-AFIR method, without any additional quantum chemical calculations. For this reaction, the MC-AFIR search found 125 unique TSs automatically. Among the 125 TSs, 19 were suggested as candidates, and finally, six including the one reported in the literature were confirmed to cause the dynamical bifurcation. The present procedure would be promising to find TSs involved in the dynamical bifurcation automatically.
采用人工力诱导反应多组分版本（MC - AFIR）方法系统地探索了2 - 乙烯基呋喃与3 - 甲氧基羰基环戊二烯酮之间的狄尔斯 - 阿尔德反应路径。在该反应中，据报道会发生一种单一过渡态（TS）与两种不同产物相关的动力学分支现象[J. B. Thomas等人，《美国化学会志》，2008年，130卷，14544 - 14555页]。在本文中，基于MC - AFIR方法，我们提出了一种系统探索所谓双峰过渡态的程序，动力学分支通过该过渡态发生。本程序从MC - AFIR方法自动反应路径搜索的日志中找到可能导致动力学分支的过渡态候选物，无需任何额外的量子化学计算。对于该反应，MC - AFIR搜索自动找到了125个独特的过渡态。在这其中125个过渡态中，可以确定有19个为候选过渡态，最后，包括文献中报道的一个在内，有六个被确认为会导致动力学分支。本程序有望自动找到涉及动力学分支的过渡态。
