An Ab Initio Study of SN2 Reactivity at C6 in Hexopyranose Derivatives. I. Influence of Dipole-dipole Interactions in the Transition Structure

Abstract

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.

Department(s)

Chemistry

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)

1089-5639

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2005, American Chemical Society (ACS), All rights reserved.

Publication Date

01 Jan 2005

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