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

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Resumen

(Chemical Equation Presented) 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.

Idioma originalEnglish
Páginas (desde-hasta)4615-4624
Número de páginas10
PublicaciónJournal of Organic Chemistry
Volumen73
N.º12
DOI
EstadoPublished - 20 jun 2008

Huella dactilar

Ethylenes
Cycloaddition
Nucleophiles
Discrete Fourier transforms
Electronic structure
Molecules

ASJC Scopus subject areas

  • Organic Chemistry

Citar esto

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abstract = "(Chemical Equation Presented) 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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T1 - Understanding the reactivity of captodative ethylenes in polar cycloaddition reactions. A theoretical study

AU - Domingo, Luis R.

AU - Chamorro, Eduardo

AU - Pérez, Patricia

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Y1 - 2008/6/20

N2 - (Chemical Equation Presented) 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.

AB - (Chemical Equation Presented) 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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