Article

 

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

 

Manuel Fernando Rubio,¹ Federico Jiménez–Cruz² and Guillermo Ramírez–Galicia³*

 

¹ Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510, Coyoacán, México DF, México.

² Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, San Bartolo Atepehuacan, 07730, México DF, México.

³ Universidad del Papaloapan, División de Estudios de Posgrado, Circuito Central 200, Parque Industrial, 68301, Tuxtepec, Oaxaca, México. e–mail: gramirez@unpa.edu.mx memorgal@gmail.com

 

Received August 12, 2010.
Accepted September 2, 2010.

 

Abstract

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.

Keywords: B3LYP/6–31+G*, MP2/6–31+G*//B3LYP/6–31+G* calculations Hammett relationship, kinetic control, thermodynamic control, [2+2] cycloaddition.

 

Resumen

Se realizó un estudio teórico al nivel de teoría DFT (B3LYP/6–31+G*) y post–Hartree–Fock (MP2/6–31+G*//B3LYP/6–31G*) para explicar el efecto del sustituyente remoto en la cicloadición [2+2] intramolecular de cetena–estireno en 2–metil–7–arilhepta–1,6–dien–1–ona p–sustituida la cual produce biciclo[3.1.1] o bici–clo[3.2.0] heptanonas de acuerdo a los resultados experimentales de Bèlanger. Se encontró que el estado de transición presenta una geometría de anillo de tres miembros, correspondiente a un estado de transición asincrónico por medio de una carga positiva incipiente. Se propone que la reacción puede ser controlada de forma cinética y termodinámica de acuerdo con los cálculos B3LYP/6–31+G*. Adicionalmente se reprodujo el valor de la constante de reacción experimental p~ –1.34.

Palabras clave: B3LYP/6–31+G*, MP2/6–31+G*//B3LYP/6–31+G* relaciones tipo Hammett, control cinético, control termodinámico, cicloadición [2+2].

 

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