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Intramolecular transacylation: fragmentation of protonated molecules via ion-neutral complexes in mass spectrometry

Authors

  • Ya-Ping Tu,

    Corresponding author
    1. Drug Metabolism and Pharmacokinetics, Genelabs Technologies, Inc., 505 Penobscot Drive, Redwood City, CA 94063, USA
    Current affiliation:
    1. DMPK, Infectious Diseases Center of Excellence for Drug Discovery, GlaxoSmithKline, 5 Moore Drive, Research Triangle Park, NC 27709, USA.
    • DMPK, Infectious Diseases Center of Excellence for Drug Discovery, GlaxoSmithKline, 5 Moore Drive, Research Triangle Park, NC 27709, USA.
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  • Yingying Huang,

    1. Scientific Instruments Division, Thermo Fisher Scientific, 355 River Oaks Parkway, San Jose, CA 95134, USA
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  • Christian Atsriku,

    1. Drug Metabolism and Pharmacokinetics, Genelabs Technologies, Inc., 505 Penobscot Drive, Redwood City, CA 94063, USA
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  • You You,

    1. Drug Metabolism and Pharmacokinetics, Genelabs Technologies, Inc., 505 Penobscot Drive, Redwood City, CA 94063, USA
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  • Jack Cunniff

    1. Scientific Instruments Division, Thermo Fisher Scientific, 355 River Oaks Parkway, San Jose, CA 95134, USA
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Abstract

An intramolecular transacylation reaction was observed in the mass spectrometry of molecules containing both benzoyl and carboxymethyl groups on an aromatic heterocyclic core. The reaction is triggered by a dissociative protonation on the heterocyclic ring at the atom (carbon or nitrogen) that bonds to the benzoyl group, leading to an intermediate ion-neutral complex. The incipient benzoyl cation in the complex migrates to attack the carboxyl group of the neutral partner at the carbonyl or hydroxyl oxygen under thermodynamic or kinetic control, respectively. Elimination of benzoic acid followed by loss of carbon monoxide takes place as a result of the transacylation. Copyright © 2009 John Wiley & Sons, Ltd.

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