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Experimental and theoretical study of the influence of the solvent on asymmetric diels—alder reactions
Author(s) -
Cativiela C.,
Garcia J. I.,
Mayoral J. A.,
Royo A. J.,
Salvatella L.,
Assfeld X.,
RuizLopez M. F.
Publication year - 1992
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610050503
Subject(s) - chemistry , cyclopentadiene , solvent effects , methyl acrylate , solvation , selectivity , solvent , acrylate , organic chemistry , computational chemistry , supermolecule , aqueous solution , diels–alder reaction , catalysis , polymer , molecule , monomer , copolymer
Rate, endo/exo and diastereofacial selectivities of the Diels–Alder reaction between cyclopentadiene and (—)‐menthyl acrylate were measured in a series of organic solvents and organic–aqueous mixtures. Regression analyses show that a model with the α empirical solvent parameter accounts for most of the changes in rates and diastereofacial selectivities, whereas in the case of the endo/exo selectivity, inclusion of the π * and δ parameters is needed. Theoretical calculations carried out on the model reaction between methyl acrylate and cyclopentadiene using dielectric continuum and supermolecule models do not clearly show the effect of the different solvation mechanisms on rate. However, they agree with the above‐mentioned influence of α and π * on the endo/exo and diastereofacial selectivities.