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Article
Formation and Stability of Oxocarbenium Ions From Glycosides
Journal of Mass Spectrometry
  • Chagit Denekamp, Technion - Israel Institute of Technology
  • Yana Sandlers, Technion - Israel Institute of Technology
Document Type
Article
Publication Date
8-1-2005
Disciplines
Abstract

Structural, protecting group and leaving group effects in the formation of oxocarbenium intermediates were studied in the gas phase. It is found that significant stabilization of oxocarbenium cations is achieved by protecting groups that interact with the cationic center via neighboring group participation despite the electron-withdrawing character of these moieties. On the other hand, ethereal protecting groups do not facilitate the formation of oxocarbenium intermediates. The experimental findings are supported by DFT calculations that show the following order of stabilization by the group adjacent to the cationic center: RCO > SiR3 > R, where R is an alkyl group. This indicates that the SN1-like mechanism that is commonly proposed for this reaction is not always valid. Moderate leaving group effect is also detected in a series of thioaryl glucopyranosides. Copyright © 2005 John Wiley & Sons, Ltd.

DOI
10.1002/jms.880
Citation Information
Chagit Denekamp and Yana Sandlers. "Formation and Stability of Oxocarbenium Ions From Glycosides" Journal of Mass Spectrometry Vol. 40 Iss. 8 (2005) p. 1055 - 1063 ISSN: 10765174
Available at: http://works.bepress.com/yana-sandlers/7/