[5,5] sigmatropic rearrangement. DFT prediction of a diradical mechanism for a Woodward-Hoffmann "allowed" thermal pericyclic reaction

被引:34
作者
Beno, BR
Fennen, J
Houk, KN [1 ]
Lindner, HJ
Hafner, K
机构
[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
[2] Tech Univ Darmstadt, Inst Organ Chem, D-64287 Darmstadt, Germany
关键词
D O I
10.1021/ja981083a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The mechanisms of the degenerate [5,5] sigmatropic rearrangements of 5,5a,10,10a-tetrahydroheptalene and (Z,Z)-1,3,7,9-decatetraene were explored with restricted and unrestricted Becke3LYP/6-31G* hybrid HF-DFT calculations. The restricted DFT wavefunctions for the synchronous, concerted transition structures for these formally Woodward-Hoffmann allowed 10-electron rearrangements are unstable with respect to unrestricted wavefunctions. A stepwise diradical mechanism is predicted for both reactions. The 9 kcal/mol preference for the [5s,5s] mechanism over the [5a,5a] pathway in the rearrangement of decatetraene results primarily from the geometric distortions that the system must adopt in the [5a,5a] transition structure. The geometric and electronic characteristics of the [5,5] and [3,3] (Cope) rearrangements are compared.
引用
收藏
页码:10490 / 10493
页数:4
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