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

Resultado de la investigación: Article

80 Citas (Scopus)

Resumen

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.

Idioma originalEnglish
Páginas (desde-hasta)4046-4053
Número de páginas8
PublicaciónJournal of Physical Chemistry A
Volumen112
N.º17
DOI
EstadoPublished - 1 may 2008

Huella dactilar

Diels-Alder reactions
butadiene
Density functional theory
density functional theory
Electrons
Nucleophiles
electrons
Cycloaddition
nucleophiles
cycloaddition
dienes
Discrete Fourier transforms
Ground state
reagents
orbitals
ground state
electronics
1,3-butadiene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

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title = "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",
abstract = "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.",
author = "Domingo, {Luis R.} and Eduardo Chamorro and Patricia P{\'e}rez",
year = "2008",
month = "5",
day = "1",
doi = "10.1021/jp711704m",
language = "English",
volume = "112",
pages = "4046--4053",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "17",

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TY - JOUR

T1 - 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

AU - Domingo, Luis R.

AU - Chamorro, Eduardo

AU - Pérez, Patricia

PY - 2008/5/1

Y1 - 2008/5/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=45249085292&partnerID=8YFLogxK

U2 - 10.1021/jp711704m

DO - 10.1021/jp711704m

M3 - Article

C2 - 18370427

AN - SCOPUS:45249085292

VL - 112

SP - 4046

EP - 4053

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 17

ER -