%0 Journal Article
%T Theoretical Study of the Electronic Effects in the Intramolecular Ketene-Styrene [2+2] Cycloaddition
%A Rubio
%A Manuel Fernando
%A Jim¨¦nez-Cruz
%A Federico
%A Ram¨ªrez-Galicia
%A Guillermo
%J Journal of the Mexican Chemical Society
%D 2010
%I Sociedad Qu¨ªmica de M¨¦xico
%X dft (b3lyp/6-31+g*) and post-hartree-fock (mp2/6-31+g*//b3lyp/6-31g*) calculations were carried out in order to explain the effect of a remote substituent in the intramolecular ketene-styrene [2+2] cycloaddition of p-substituted 2-methyl-7-arylhepta-1,6-dien-1-one which produces the bicycle[3.1.1] or the bicy-cle[3.2.0] heptanones according to b¨¨langer experimental results. the transition state geometries were found as an asynchronous process with a three-member ring structure and an incipient positive charge development. kinetic and thermodynamic controls were proposed at b3lyp/6-31+g* to determine which product is most likely to form in a competence reaction. in addition, the value of the ¦Ñ experimental reaction constant was reproduced, ¦Ñ ~ -1.34.
%K b3lyp/6-31+g*
%K mp2/6-31+g*//b3lyp/6-31+g* calculations hammett relationship
%K kinetic control
%K thermodynamic control
%K [2+2] cycloaddition.
%U http://www.scielo.org.mx/scielo.php?script=sci_abstract&pid=S1870-249X2010000400006&lng=en&nrm=iso&tlng=en