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.
Rapid Commun Mass Spectrom. 2011 Apr 30;25(8):1061-9. doi: 10.1002/rcm.4955. Epub 2011 Mar 29.
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.
采用电喷雾多级质谱（ESI-MS(n)）和 B3LYP/6-31G(d)水平的中等理论计算，研究了氨基酸甲酯膦酸酯衍生物的质谱行为。发现了一种新的甲基向磷酰基迁移并形成中间环状氨酰基磷酰胺的过程。通过高分辨串联质谱证实了重排离子的建议结构。提出了一种涉及五配位磷酸-羧酸磷酸酐的可能机制，其中金属离子与磷酰基和羰基的配位以及磷酰基的固有性质可能是导致这种新型迁移的关键因素。
