1-Acetylvinyl acrylates: New captodative olefins bearing an internal probe for the evaluation of the relative reactivity of captodative against electron-deficient double bonds in Diels-Alder and Friedel-Crafts reactions

Rafael Herrera, Hugo A. Jiménez-Vázquez, Francisco Delgado, Björn C.G. Söderberg, Joaquín Tamariz

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemoselectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/ 6-311G(d,p) calculations. ©2005 Sociedade Brasileira de Química.
Original languageAmerican English
Pages (from-to)456-466
Number of pages11
JournalJournal of the Brazilian Chemical Society
DOIs
StatePublished - 1 Jan 2005

Fingerprint

Bearings (structural)
Friedel-Crafts reaction
Acrylates
Cycloaddition
Alkenes
Crotonates
Cyclopentanes
Stereoselectivity
Thiophenes
Molecules
Electrons
Acrylics
Esters
Substrates

Cite this

@article{bcb873c273c04b75ba3eae3ff536ee70,
title = "1-Acetylvinyl acrylates: New captodative olefins bearing an internal probe for the evaluation of the relative reactivity of captodative against electron-deficient double bonds in Diels-Alder and Friedel-Crafts reactions",
abstract = "The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemoselectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/ 6-311G(d,p) calculations. {\circledC}2005 Sociedade Brasileira de Qu{\'i}mica.",
author = "Rafael Herrera and Jim{\'e}nez-V{\'a}zquez, {Hugo A.} and Francisco Delgado and S{\"o}derberg, {Bj{\"o}rn C.G.} and Joaqu{\'i}n Tamariz",
year = "2005",
month = "1",
day = "1",
doi = "10.1590/S0103-50532005000300021",
language = "American English",
pages = "456--466",
journal = "Journal of the Brazilian Chemical Society",
issn = "0103-5053",
publisher = "Sociedade Brasileira de Quimica",

}

TY - JOUR

T1 - 1-Acetylvinyl acrylates: New captodative olefins bearing an internal probe for the evaluation of the relative reactivity of captodative against electron-deficient double bonds in Diels-Alder and Friedel-Crafts reactions

AU - Herrera, Rafael

AU - Jiménez-Vázquez, Hugo A.

AU - Delgado, Francisco

AU - Söderberg, Björn C.G.

AU - Tamariz, Joaquín

PY - 2005/1/1

Y1 - 2005/1/1

N2 - The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemoselectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/ 6-311G(d,p) calculations. ©2005 Sociedade Brasileira de Química.

AB - The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemoselectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/ 6-311G(d,p) calculations. ©2005 Sociedade Brasileira de Química.

U2 - 10.1590/S0103-50532005000300021

DO - 10.1590/S0103-50532005000300021

M3 - Article

SP - 456

EP - 466

JO - Journal of the Brazilian Chemical Society

JF - Journal of the Brazilian Chemical Society

SN - 0103-5053

ER -