FACIAL DIFFERENTIATION IN DIELS-ALDER REACTIONS TO DISSYMMETRIC CYCLOHEXA-1,3-DIENES

被引：41

作者：

COXON, JM

MACLAGAN, RGAR

MCDONALD, DQ

STEEL, PJ

机构：

[1] Department of Chemistry, University of Canterbury, Christchurch

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 07期

关键词：

D O I：

10.1021/jo00007a051

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reactions of 2a-c with maleic anhydride (MA) and benzoquinone (BQ) show strong preference for addition to the ''carbonyl'' face of the diene. For dimethyl acetylenedicarboxylate (DMAD), attack from this face decreases with successive methylidene substitution while for N-phenyl-1,2,4-triazolinedione (PTAD) the reverse occurs. The consequence of orbital tilting and transition-state steric and torsional interactions cannot alone account for the facial selectivity for the reactions with DMAD and PTAD. Unfavorable orbital interaction of the closed shells of the carbonyl(s) and methylidene(s) syn to the incoming orthogonal pi orbital of DMAD is considered to be important.

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页码：2542 / 2549

页数：8

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