Understanding the reactivity of captodative ethylenes in polar cycloaddition reactions.: A theoretical study

被引:927
作者
Domingo, Luis R. [1 ]
Chamorro, Eduardo [2 ]
Perez, Patricia [2 ]
机构
[1] Univ Valencia, Dept Quim Organ, E-46100 Burjassot, Spain
[2] Univ Andres Bello, Fac Ecol & Recursos Nat, Lab Quim Teor, Dept Ciencias Quim, Santiago 8370146, Chile
关键词
D O I
10.1021/jo800572a
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The electrophilic/nucleophilic character of a series of captodative (CD) ethylenes involved in polar cycloaddition reactions has been studied using DFT methods at the B3LYP/6-31G(d) level of theory. The transition state structures for the electrophilic/nucleophilic interactions of two CD ethylenes toward a nucleophilically activated ethylene, 2-methylene-1,3-dioxolane, and an electrophilically activated ethylene, 1,1-dicyanoethyelene, have been studied, and their electronic structures have been characterized using both NBO and ELF methods. Analysis of the reactivity indexes of the CD ethylenes explains the reactivity of these species. While the electrophilicity of the molecules accounts for the reactivity toward nucleophiles, it is shown that a simple index chosen for the nucleophilicity, N, based on the HOMO energy is useful explaining the reactivity of these CD ethylenes toward electrophiles.
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页码:4615 / 4624
页数:10
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