An understanding of the electrophilic/nucleophilic behavior of electro-deficient 2,3-disubstituted 1,3-butadienes in polar Diels-Alder reactions.: A density functional theory study

被引：106

作者：

Domingo, Luis R. ^{[1
]}

Chamorro, Eduardo ^{[2
]}

Perez, Patricia ^{[2
]}

机构：

[1] Univ Valencia, Dept Quim Organ, E-46100 Valencia, Spain

[2] Univ Andres Bello, Fac Ecol & Recursos Nat, Lab Quim Teor, Dept Ciencias Quim, Santiago 8370146, Chile

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2008年 / 112卷 / 17期

关键词：

D O I：

10.1021/jp711704m

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The electrophilic/nucleophilic behavior of dimethyl 2,3-dimethylenesuccinate 1, an electron-deficient 2,3-disubstituted 1,3-butadiene, in polar Diels-Alder reactions has been studied using DFT methods at the B3LYP/6-31G(d) level of theory. The electronic nature of bonding of the transition structures involved in the cycloaddition reactions of the diene 1 toward the nucleophilically activated dienophile 6 and the strong electrophilically activated dienophile 7 has been carefully examined within the natural bond orbital (NBO) and the topological analysis of the electron localization function (ELF) frameworks. Additionally, a study of the global electrophilicity pattern of the reagents at the ground state was performed. This evidence allows us to rationalize the participation of electron-deficient 2-susbtituted and 2,3-disubstituted 1,3-butadienes as nucleophiles in polar Diels-Alder reactions.

引用

页码：4046 / 4053

页数：8

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