title: 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.
abstract: 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.
authors: Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, PR China.
authors: Xiang
authors: X
authors: Gao
authors: Gangtian
authors: G
authors: Zhu
authors: Zhiping
authors: Z
authors: Zeng
authors: Weizhu
authors: W
authors: Chen
authors: Zhiwei
authors: Z
authors: Lin
authors: Yan
authors: Y
authors: Liu
authors: Pengxiang
authors: P
authors: Xu
authors: Yufen
authors: Y
authors: Zhao
mesh_terms: D000577:Amides / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D009705:Nucleosides / Q000737:chemistry*; D010756:Phosphoric Acids / Q000737:chemistry*; D018894:Reverse Transcriptase Inhibitors / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D013816:Thermodynamics
chemical_list: D000577:Amides; D000596:Amino Acids; D009705:Nucleosides; D010756:Phosphoric Acids; D018894:Reverse Transcriptase Inhibitors; C011067:phosphoramidic acid