Theoretical Study of the Electronic Effects in the Intramolecular Ketene-Styrene [2+2] Cycloaddition

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 bèlanger 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 ρ experimental reaction constant was reproduced, ρ ~ -1.34.