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A novel methyl migration to the phosphoryl group with the formation of cyclic aminoacylphosphoramidates in electrospray ionization tandem mass spectra of amino acid ester phosphoramidates of antiviral nucleosides
Author(s) -
Gao Xiang,
Zhu Gangtian,
Zeng Zhiping,
Chen Weizhu,
Lin Zhiwei,
Liu Yan,
Xu Pengxiang,
Zhao Yufen
Publication year - 2011
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.4955
Subject(s) - chemistry , phosphoramidate , electrospray ionization , tandem mass spectrometry , electrospray , mass spectrum , mass spectrometry , phosphate , medicinal chemistry , stereochemistry , ion , organic chemistry , chromatography
The mass spectral behavior of amino acid methyl ester phosphoramidate derivatives have been investigated using electrospray ionization multistage mass spectrometry (ESI‐MS n ) and moderate theoretical calculations at the B3LYP/6‐31G(d) level. A novel methyl group migration to the phosphoryl group with the formation of the intermediate cyclic aminoacylphosphoramidate was found. The proposed structures of the rearrangement ions were confirmed by high‐resolution tandem mass spectrometry. A possible mechanism involving the pentacoordinate phosphoric‐carboxylic phosphate anhydride was proposed, in which the metal ion coordination with the phosphoryl and carbonyl groups and the intrinsic properties of phosphoryl group might be the key factors responsible for this novel migration. Copyright © 2011 John Wiley & Sons, Ltd.