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Mass spectral study of cyclic alkaneboronates of sugar phosphates. Evidence of interaction between the phosphate group and boron under electron‐impact conditions
Author(s) -
Wiecko Jacek,
Sherman William R.
Publication year - 1975
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210101111
Subject(s) - chemistry , ion , boron , fragmentation (computing) , galactose , sugar , phosphate , sugar phosphates , mass spectrometry , deuterium , butane , electron ionization , stereochemistry , medicinal chemistry , organic chemistry , chromatography , catalysis , physics , quantum mechanics , computer science , ionization , operating system
Cyclic butane‐ and methaneboronic esters of dimethylphosphates of glucose, galactose, mannose, fructose and methyl gluconate have been examined by mass spectrometry. High resolution information and deuterium labeling of all six carbons of glucose, as well as of the methylphosphate groups, permits elucidation of the origin of various ions, which can be grouped according to their probable mechanism of formation. In each case, the intensity of the [M – R] + ion can be rationalized, in stereochemical terms, by the ease with which incipient positive charge on boron can be stabilized by the phosphate group. This interaction also gives rise to rearrangement ions containing a BOP linkage. Other effects of structure on fragmentation pattern are discussed. Retention of specific portions of the glucose skeleton in ions with clearly defined label shift behavior, as well as the preservation of intact sugar moieties in intense [M – R] + ions, suggests applications for stable isotope analyses. These are discussed in terms of their advantages over silicon‐containing derivatives.