Mass spectral study of cyclic alkaneboronates of sugar phosphates. Evidence of interaction between the phosphate group and boron under electron‐impact conditions

Wiecko, Jacek; Sherman, William R.

doi:10.1002/oms.1210101111

Cited by 19 publications

(7 citation statements)

References 33 publications

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“…The 6-acetylpyranose molecule, after loss of the neutral fragment corresponding to the fragment a bearing C-l and -2, or C-3 and -4, can, among other possible processes, eliminate acetic acid, giving a fragment ion at m/e 168, or, alternatively, can eject the butyl radical if interaction between the acetyl group and boron is stereochemically favored, giving rise to a peak at m/e 171. Equation 3 (3) process for 7. It is clear that in molecules 7 and 9 either process is possible depending on which carbons are involved in the initial extrusion of the neutral fragment corresponding to a.…”

Section: Resultsmentioning

confidence: 99%

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Boroacetylation of carbohydrates. Correlations between structure and mass spectral behavior in monoacetylhexose cyclic boronic esters

Wiecko¹,

Sherman²

1976

J. Am. Chem. Soc.

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The interaction of an acetyl moiety with boron accompanied by the loss of alkyl radical is shown to occur following electron beam ionization in the mass spectrometer. This is similar to the interaction of phosphate with boron previously shown to occur in alkaneboronic esters of certain sugar phosphate dimethyl esters. I n the case of acetates, the interacting moiety can frequently be introduced into a hexose in an equilibrium reaction in which treatment with an alkaneboronic acid is followed by acetylation of the remaining hydroxyl. The interaction, following ionization, is shown to be localized to the adjacent cyclic boronate in the case of D-glucose and D-galactose alkaneboronate acetates. The use of this interaction as a stereochemically sensitive probe of structure is demonstrated. In the course of this work, the cyclic bis(a1kaneboronates) of monoacetylated Dglucose, D-galactose, D-mannose, D-idose, D-allOSe, D-altrose, D-talose, D-glucose, D-fructose, D-sorbose, D-tagatose, and Dpsicose were examined by mass spectrometry. High-resolution data, as well as specific deuterium labeling of the six carbon atoms of glucose, reveal the origin of characteristic classes of ions.The preparation of a substance for mass spectral analysis by gas chromatography-mass spectrometry (GC-MS) is a n opportunity to exercise some control over the fragmentation process of the ionized molecule. Cyclic boronic esters of carbohydrates are useful because they have steric requirements for their formation and thus confer an additional degree of specificity on stereoisomers. In this respect they resemble isopropylidene derivatives. The boronic esters, however, are rapidly formed in reactions which give quantitative conversions with many sugars.The isopropylidene ketals2 have a further similarity to the alkaneboronates in that both are capable, on electron beam ionization, of losing an alkyl side chain from the derivative moiety to produce a high abundance even electron ion. This similarity is only a formal one, however, because of the different electronic structures of boron and carbon. In the isopropylidene case, the radical loss from carbon produces an ion that is readily stabilized by the 1,3-dioxolane structure. The situation with boron is very different in that the cyclic boronate is incapable of stabilizing the charge left by the departing radical without the intervention of another functionality. W e have reported on this interaction in the case of cyclic alkaneboronates of sugar phosphates3 In the latter the phosphate is the interacting moiety which, when favored by proximity, supports the formation of high abundance [M -alkyl]+ ions.The principal subject of the present paper is the nature of this process in monoacetates of sugar alkaneboronates. The interaction of the acetate with boron appears weaker than that of phosphate, thus more stereoselective, and therefore a more useful probe of structure. Furthermore, the single acetyl moiety is easily introduced in equilibrium reactions with sugars and alkaneboronic acids. The reactio...

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Section: Resultsmentioning

confidence: 99%

“…We have reported on this interaction in the case of cyclic alkaneboronates of sugar phosphates. 3 In the latter the phosphate is the interacting moiety which, when favored by proximity, supports the formation of high abundance [Malkyl]+ ions.…”

mentioning

confidence: 99%

Boroacetylation of carbohydrates. Correlations between structure and mass spectral behavior in monoacetylhexose cyclic boronic esters

Wiecko¹,

Sherman²

1976

J. Am. Chem. Soc.

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“…The interaction between the nitro group and the boron proposed in the first step of Scheme 12 is of the same type. [33][34][35][36] (3) Selected metastable ion monitoring during GC is a well-known and selective technique for quantification of organic substances such as steroids37 and cann a b i n~i d s .~~ For these analyses, the analyser is static. This paper is the first publication to describe computerized acquisition of full linked scan spectra during GC/MS with a magnetic sector instrument, a technique which permits separation and mass spectral differentiation of isomeric substances in a mixture.…”

Section: Discussionmentioning

confidence: 99%

Derivatization and mass spectrometric investigations of substituted benzeneboronic acids. The use of linked scanning during gas chromatography mass spectrometry

Longstaff

Rose

1982

Org. Mass Spectrom.

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Substituted benzeneboronic acids are important intermediates in the synthesis of support matrices for Srsnity chromatography but their analysis by mass spectrometry is hindered by thermal reactions in the ion source. A simple derivatization with 1,2-or 1,3-diols removes this daculty and imparts sufficient volatility for application of gas chromatography/mass spectrometry. The mass spectra of the resulting boronate esters are discussed with reference to high resolution measurements, isotope labelling studies and observation of metastable ions. ortho Substhents are shown to interact strongly during fragmentation. Linked scanning at constant BIE was used to characterize fragmentation pathways and the compatibility of linked scanning and GC/MS is reported.

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“…27). 105,106 This property was notably used to probe sites of phosphorylation in peptides and nucleotides. [107][108][109][110][111]…”

Section: Interaction With the Internucleosidic Linkagementioning

confidence: 99%

Boron and nucleic acid chemistries: merging the best of both worlds

2013

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At the intersection of nucleic acid and boron chemistries lies a thriving world of possibilities. During the past decades, the merging of these research domains has led to fascinating discoveries in different fields ranging from material to medical sciences. In recent years the interplay of these two worlds has gained a lot of attention, as can be judged by the increasing number of articles in which boron and nucleic acids stand out for their potential medicinal, biotechnological or analytical applications. In this review, we present an outline of this crossroads by focusing on both the interaction of boronated compounds with nucleic acids and the modification of nucleic acids by boron containing moieties.

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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

Cited by 19 publications

References 33 publications

Boroacetylation of carbohydrates. Correlations between structure and mass spectral behavior in monoacetylhexose cyclic boronic esters

Boroacetylation of carbohydrates. Correlations between structure and mass spectral behavior in monoacetylhexose cyclic boronic esters

Derivatization and mass spectrometric investigations of substituted benzeneboronic acids. The use of linked scanning during gas chromatography mass spectrometry

Boron and nucleic acid chemistries: merging the best of both worlds

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