Polar Bromination of Cyclopropane:  A DFT Study

Hitherto the polar addition of bromine to cyclopropane has been considered as a two-step process. Current calculations have established the energetics for the proposed cation−anion pairs required by these mechanisms. An energetically lower pathway is proposed here in the form of a syn-cycloaddition...

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Bibliographic Details
Published in:Journal of organic chemistry 2000-04, Vol.65 (7), p.2192-2194
Main Authors: Coxon, James M, Smith, William B
Format: Article
Language:English
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Summary:Hitherto the polar addition of bromine to cyclopropane has been considered as a two-step process. Current calculations have established the energetics for the proposed cation−anion pairs required by these mechanisms. An energetically lower pathway is proposed here in the form of a syn-cycloaddition process. Compared to the two-step process, a significantly lower activation enthalpy for this process has been found. The stereochemical consequences of the cyclic mechanism are retention−retention for the two adding moieties. This result is consistent with published experimental data on the bromination of a deuterated cyclpropane.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo991831u