Journal of the Chemical Society. Perkin transactions II p. 923 - 930 (1986)
Update date:2022-08-04
Topics:
Durham, Dana
Kingsbury, Charles A.
The stereochemistry and kinetics of acid-catalysed ring-opening reactions of epoxides are reported.Predominant inversion is found in the usual hydroxylic solvents.As the nucleophilicity of the solvent diminishes and acidity increases, the stereochemistry changes to predominant retention.Electron-donating substituents also tend to favour retention.In mixed solvents, the solvent microstructure is altered, leading to net retention for nucleophiles such as methanol.The exception is dioxane-methanol, which gives enhanced inversion.Molecular mechanics calculations indicate an electrostatic preference for the retention route, but a steric preference for inversion.The activation parameters indicate a negative entropy for both inversion and retention paths.Possible reasons are discussed for the entropy of the retention route being in the range normally found for A2 reactions.
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