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Ketalization of gaseous acylium ions

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Journal of the American Society for Mass Spectrometry

Abstract

A novel reaction of gaseous acylium ions: ketalization with diols and analogs, has been systematically studied via pentaquadrupole MS2 and MS3 experiments and ab initio calculations. A variety of α,β-diols and their amino, thiol, ether, and thioether analogs have been tested for reactivity, mechanism evaluation, site selectivity, and for the effects of α- and β-interfunctional separation. As for condensed-phase ketalization of neutral carbonyl compounds followed by hydrolysis, gaseous acylium ions are chemically deactivated in the form of cyclic ionic ketals by ketalization, and are efficiently released via on-line collision-induced dissociation. Ketalization of acylium ions is shown to identify and structurally characterize α,β-diols and their analogs, and to distinguish regioisomers. Diastereomers can also be distinguished, as illustrated for cis and trans 1,2-diaminocyclohexane. The MS2 and MS3 data together with 18O-labeling and ab initio calculations establish for acylium ion ketalization a mechanism of anchimeric assistance with participation of the neighboring acyl group.

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Authors and Affiliations

  1. Institute of Chemistry, State University of Campinas, CP 6154, 13083-970, Campinas, SP, Brazil

    Luis Alberto B. Moraes & Marcos N. Eberlin

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  1. Luis Alberto B. Moraes
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  2. Marcos N. Eberlin
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Correspondence to Marcos N. Eberlin.

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Moraes, L.A.B., Eberlin, M.N. Ketalization of gaseous acylium ions. J Am Soc Mass Spectrom 12, 150–162 (2001). https://doi.org/10.1016/S1044-0305(00)00211-7

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  • DOI: https://doi.org/10.1016/S1044-0305(00)00211-7

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