Rearrangement of Protonated Propene Oxide to Protonated Propanal

Calculations at the MP2/6-31G*//MP2/6-31G* level show there are concerted asynchronous pathways connecting protonated propene oxide and protonated propanal. With cleavage of the C−O bond of protonated propene oxide, the preference for rotation of oxygen away from the more hindered face of the oxiran...

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Bibliographic Details
Published in:Journal of the American Chemical Society 1997-05, Vol.119 (20), p.4712-4718
Main Authors: Coxon, James M, Maclagan, Robert G. A. R, Rauk, Arvi, Thorpe, Aaron J, Whalen, Dale
Format: Article
Language:English
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Summary:Calculations at the MP2/6-31G*//MP2/6-31G* level show there are concerted asynchronous pathways connecting protonated propene oxide and protonated propanal. With cleavage of the C−O bond of protonated propene oxide, the preference for rotation of oxygen away from the more hindered face of the oxirane plane containing the methyl group is quantified as 2 kcal/mol. This pathway involves two distinct steps; first, rupture of the oxirane and, second, hydride migration. The latter does not commence until rupture of the C−O bond is complete. The combination of these two steps defines a concerted asynchronous rearrangement pathway. The reaction is predicted to show a 20:1 preference for migration of the proton trans to the methyl over the cis.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja963057n