TY - JOUR
T1 - Structural, spectroscopic, and theoretical study of 1-acetylvinyl p-nitrobenzoate, a highly reactive and selective captodative olefin in cycloaddition reactions
AU - Jiménez-Vázquez, Hugo A.
AU - Ochoa, María E.
AU - Zepeda, Gerardo
AU - Modelli, Alberto
AU - Jones, Derek
AU - Mendoza, Jorge A.
AU - Tamariz, Joaquín
PY - 1997/12/18
Y1 - 1997/12/18
N2 - X-ray crystallography, variable temperature 1H NMR and nuclear Overhauser effect experiments, and ab initio calculations provided evidence of the s-trans preferential conformation of captodative olefin 1-acetylvinyl p-nitrobenzoate (1a) in solid, solution, and gas phases. The reactivity of 1a in cycloaddition reactions was rationalized under the basis of experimental ionization energy and electron affinity parameters. Correlation of the latter with the frontier molecular orbitals, calculated at the ab initio 3-21G and 6-31G* levels, suggests a nonsignificant effect of the electron-donor group upon control of the reactivity and regioselectivity of these olefins in Diels-Alder reactions.
AB - X-ray crystallography, variable temperature 1H NMR and nuclear Overhauser effect experiments, and ab initio calculations provided evidence of the s-trans preferential conformation of captodative olefin 1-acetylvinyl p-nitrobenzoate (1a) in solid, solution, and gas phases. The reactivity of 1a in cycloaddition reactions was rationalized under the basis of experimental ionization energy and electron affinity parameters. Correlation of the latter with the frontier molecular orbitals, calculated at the ab initio 3-21G and 6-31G* levels, suggests a nonsignificant effect of the electron-donor group upon control of the reactivity and regioselectivity of these olefins in Diels-Alder reactions.
UR - http://www.scopus.com/inward/record.url?scp=0031355495&partnerID=8YFLogxK
U2 - 10.1021/jp972707m
DO - 10.1021/jp972707m
M3 - Artículo
SN - 1089-5639
VL - 101
SP - 10082
EP - 10089
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 51
ER -