Theoretical study of endo selectivity in the Diels-Alder reactions between butadienes and cyclopropene

被引:28
作者
Imade, M [1 ]
Hirao, H [1 ]
Omoto, K [1 ]
Fujimoto, H [1 ]
机构
[1] Kyoto Univ, Div Mol Engn, Kyoto 6068501, Japan
关键词
D O I
10.1021/jo990440c
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The endo selectivity in the Diels-Alder reactions of some substituted butadienes with cyclopropene has been investigated theoretically. Electron delocalization between a diene and the dienophile has been presented in terms of pairs of interaction orbitals. In addition to the principal orbital interactions to form new sigma bonds between the diene and the dienophile, the cyclopropene occupied interaction orbital shows significant amplitudes on the methylenic hydrogens to overlap in phase with the paired unoccupied interaction orbital of butadiene at the backbone C-2 and C-3 carbons. The contribution of this secondary orbital interaction to the stabilization of the transition state has been estimated numerically. It has been demonstrated that neither electron delocalization nor the electrostatic interaction interprets preference of the endo-addition over the exo-addition, but the sum of the two terms has been found to show a correlation with the difference in the barrier heights for the two modes of cycloadditions.
引用
收藏
页码:6697 / 6701
页数:5
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