A novel hydrogen migration of dialkylphosphonic acid esters using electrospray ionization tandem mass spectrometry
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In this paper, attention is focused on analysis of the fragmentation of alpha-hydroxy-beta-amino phosphonate esters designed as inhibitors of protein kinase A. An interesting proton migration mechanism in the cleavage of the P-C bond is investigated by electrospray ionization tandem mass spectrometry. A possible rearrangement mechanism is proposed and verified by high-resolution mass spectra using isotope deuterium/hydrogen-exchange technology and additionally checked by detailed DFT calculation based on Gaussian software. The result clearly indicates that this mechanism proceeds by a five-membered ring concerted transition state with activation energy 11.3 kcal mol(-1) for the compound 3f. The overall reaction is endothermic with an energy 13.2 kcal mol(-1). The effect of different substituents and different metal ions for rearrangement of these esters is studied by experiment and theory. It is concluded that this rearrangement process is energetically unfavorable and hence only occurs in the mass spectrometer. Copyright (C) 2011 John Wiley & Sons, Ltd.
CitationRAPID COMMUNICATIONS IN MASS SPECTROMETRY，2011,25（21）：3314-3322