Ambimodal Trispericyclic Transition State and Dynamic Control of Periselectivity
Ambimodal Trispericyclic Transition State and Dynamic Control of Periselectivity
复制标题
双峰三周环过渡态和近选择性动态控制
DOI：
10.1021/jacs.8b12674
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发表时间：
2019
影响因子：
15
通讯作者：
Houk K. N.
中科院分区：
文献类型：
--
作者：
Xue Xiao-Song;Jamieson Cooper S.;Garcia-Borras Marc;Dong Xiaofei;Yang Zhongyue;Houk K. N.
本文报道了8，8-二取代七富烯与6，6-二甲基富烯反应中的一个双峰三配位环过渡态，该过渡态导致[6+4]-、[4+6]-和[8+2]-环加合物。用密度泛函理论计算了这些反应的势能面。准经典直接分子动力学模拟给出了这些反应中预期产物的比例信息。
We report an ambimodal trispericyclic transition state leading to [6+4]-, [4+6]-, and [8+2]-cycloadducts in the reactions of 8,8-disubstituted heptafulvenes with 6,6-dimethylfulvene. The potential energy surfaces for these reactions were explored with ωB97X-D density functional theory. Quasi-classical direct molecular dynamics simulations gave information on the ratios of products expected in these reactions.