Formation and Stability of Oxocarbenium Ions From Glycosides

Document Type

Article

Publication Date

8-1-2005

Publication Title

Journal of Mass Spectrometry

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

Volume

40

Issue

8

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