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


  • Manuel Fernando Rubio Universidad Nacional Autónoma de México
  • Federico Jiménez-Cruz Instituto Mexicano del Petróleo
  • Guillermo Ramírez-Galicia Universidad del Papaloapan



B3LYP/6-31 G*, MP2/6-31 G*//B3LYP/6-31 G* calculations Hammett relationship; kinetic control; thermodynamic control; [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 bicycle [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.


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Author Biographies

Manuel Fernando Rubio, Universidad Nacional Autónoma de México

Instituto de Química

Guillermo Ramírez-Galicia, Universidad del Papaloapan

División de Estudios de Posgrado


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