THE COPE REARRANGEMENT REVISITED
THE COPE REARRANGEMENT REVISITED
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DOI：
10.1021/ja00026a007
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发表时间：
1991-12-18
影响因子：
15
通讯作者：
DAVIDSON, ER
中科院分区：
文献类型：
--
作者：
DUPUIS, M;MURRAY, C;DAVIDSON, ER
利用CASSCF波函数和6- 31 G ~* 基组，我们在势能面上找到了几个科普重排的稳定点。在这个理论水平上，我们发现通过对称的芳香族过渡态的同步路径和通过对称的biradicaloid中间体的不对称过渡态的非协调路径。在零点和热校正之后，两条路径都是可能的。对电子相关性的更详细描述并不能得出对这两种路径的明确偏好。
Using a CASSCF wave function and a 6-31G* basis set we have located several stationary points on the potential energy surface for the Cope rearrangement. At this level of theory we find both a synchronous path through a symmetrical aromatic transition state and a non-concerted path through a disymmetrical transition state followed by a symmetrical biradicaloid intermediate. After zero-point and thermal corrections both paths appear possible. A more elaborate description of electron correlation does not yield a clear preference for either path.