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Prediction of solvent effect on the reaction rate and endo / exo selectivity of a Diels–Alder reaction using molecular surface electrostatic potential
Author(s) -
Gholami M. R.,
Talebi B. A.
Publication year - 2003
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.647
Subject(s) - chemistry , diastereomer , selectivity , solvent , solvent effects , reaction rate constant , reaction rate , computational chemistry , diels–alder reaction , hydrogen bond , organic chemistry , kinetics , molecule , catalysis , physics , quantum mechanics
Molecular surface electrostatic potential was used to predict the solvent effect on the reaction rate, endo / exo selectivity and diastereomeric excess of a Diels–Alder reaction. It is shown that these quantities can be expressed in terms of molecular surface electrostatic potentials of solvents which are obtained computationally by the HF/6–31++G* procedure. Regression analyses and an experimental database are used to obtain analytical representation of rate constant, endo / exo selectivity and diastereomeric excess. The models obtained show that the hydrogen bond donor ability of solvents on the above mentioned properties is substantial, whereas solvophobicity only affects the reaction rate and endo / exo selectivity of the reaction. Copyright © 2003 John Wiley & Sons, Ltd.