AB-INITIO STUDY OF THE DIELS-ALDER REACTION BETWEEN PHOSPHOLES AND ETHYNE

被引:33
作者
BACHRACH, SM
机构
[1] Department of Chemistry, Northern Illinois University, DeKalb
关键词
D O I
10.1021/jo00096a055
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The reaction of cyclopentadiene with ethyne (reaction 1) and 1H-, 2H-, and 3H-phosphole with ethyne (reactions 2-4) were examined at the MP4SDQ/6-31G*//MP2/6-31G* level. The quality of this computational level was evaluated by comparison of the geometries and energetics of reaction 1 with experimental results. The activation energies of reactions 1-4 are 27.94, 30.62, 17.93, and 28.14 kcal mol(-1). These reactions all proceed through a common mechanism-the classic concerted [4 + 2] cycloaddition-as determined by analysis of the geometry, activation energy, and electron distribution. These calculations are then used to evaluate the mechanistic proposal of Mathey concerning the reactions of substituted 1H-phosphole with alkynes.
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页码:5027 / 5033
页数:7
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