An Ab Initio Study of SN2 Reactivity at C6 in Hexopyranose Derivatives. I. Influence of Dipole-dipole Interactions in the Transition Structure
It is widely accepted that dipole-dipole interactions in the SN2 transition structure can play a dominant role in determining reaction rates. a model of this type was proposed some years ago to explain the remarkably low reactivity of galactopyranose-6-O-sulfonates toward SN2 displacement, and similar arguments have recently been restated in the context of gas-phase reactions. in this paper, we present ab initio calculations (B3LYP/6-31+G(d,p)) on model structures and an analysis of charge densities using the theory of atoms in molecules. We find that the maximum possible impact of local dipole-dipole interactions is insufficient to account for the observed reactivity differences.
R. Dawes et al., "An Ab Initio Study of SN2 Reactivity at C6 in Hexopyranose Derivatives. I. Influence of Dipole-dipole Interactions in the Transition Structure," Journal of Physical Chemistry A, vol. 109, no. 1, pp. 213-217, American Chemical Society (ACS), Jan 2005.
The definitive version is available at http://dx.doi.org/10.1021/jp0372892
Keywords and Phrases
Dipole-dipole interactions; Galacto-configured sulfonates; Hexopyranose derivatives; Transition structure, Chemical bonds; Chemical reactions; Chloride minerals; Electric charge; Fluorine; Hydroxylation; Integration; Mathematical models, Derivatives, carbohydrate; carbon, article; chemical structure; chemistry; computer simulation, Carbohydrates; Carbon; Computer Simulation; Models, Molecular; Molecular Structure
International Standard Serial Number (ISSN)
Article - Journal
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