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Synthesis of 4‐ and 10‐deuterated neryl and geranyl‐β‐D‐glucosides and their use in corroboration of a mechanism proposed for the fragmentation of heterosides in tandem mass spectrometry
Author(s) -
Salles Christian,
Jallageas JeanClaude,
Beziat Yves,
Cristau HenriJean
Publication year - 1992
Publication title -
journal of labelled compounds and radiopharmaceuticals
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.432
H-Index - 47
eISSN - 1099-1344
pISSN - 0362-4803
DOI - 10.1002/jlcr.2580310104
Subject(s) - chemistry , deuterium , nerol , fragmentation (computing) , geraniol , hydride , double bond , mass spectrometry , tandem mass spectrometry , wittig reaction , ketone , stereochemistry , organic chemistry , chromatography , hydrogen , physics , quantum mechanics , computer science , essential oil , operating system
In order to corroborate a mechanisms proposed for the fragmentation of the molecular ion of heterosides, involving a hydride migration from the aglycome to the osidic unit, the 4‐[ 2 H 2 ]‐10‐[ 2 H 3 ]‐labelled neryl and geranyl‐β‐D‐glucosides 9 and 10 have been synthesised. Deuterated ketone 1 was prepared in >99% isotopic abundance by base catalysed exchange with [ 2 H 2 ]‐water, and was reacted under Wittig‐Horner conditions furnishing the corresponding α, β‐unsaturated esters 3 and 4 . Selective reduction of the ester group can be performed with DIBAl‐H, whereas LiAlH 4 give a secondary reduction of the CC double bond. The published procedure (13) for the β‐D‐glucosidation of alochols has been modified in order to optimise conditions on the deuterated nerol and geraniol. By comparison of collision spectra (NICI/CAD) of pure deuterated and undeuterated neryl and geranyl‐β‐D‐glucosides the proposed fragmentation mechanism is fully corroborated.