Cui Juntao, Gao Xiang, Fan Aiting, Zhang Shuangyan, Liu Yan, Xu Pengxiang, Zhao Yufen
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.
Eur J Mass Spectrom (Chichester). 2011;17(2):187-95. doi: 10.1255/ejms.1111.
Several amino acid phosphorodiamidate derivatives of d4T as anti-HIV prodrugs were synthesized and investigated using electrospray ionization multistage tandem mass spectrometry (ESI-MS(n)). A novel methyl group migration in gas phase was observed in ESI-MS(2) of the sodium adducts of amino acid methyl ester of phosphorodiamidates of 2',3'-didehydro-2',3'-dideoxythymidine (d4T). 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 a seven-membered ring intermediate was formed by coordination with the metal ion between the phosphoryl group and carbonyl oxygen atom. Thus, the intrinsic properties of phosphoryl group might be the key factors responsible for this migration.
合成了几种作为抗艾滋病毒前药的2',3'-二脱氢-2',3'-二脱氧胸苷（d4T）的氨基酸磷二酰胺酯衍生物，并采用电喷雾电离多级串联质谱法（ESI-MS(n)）进行了研究。在2',3'-二脱氢-2',3'-二脱氧胸苷（d4T）的氨基酸甲酯磷二酰胺酯的钠加合物的ESI-MS(2)中观察到一种新的气相甲基迁移。通过高分辨率串联质谱法证实了重排离子的推测结构。提出了一种涉及五配位磷 - 羧基磷酸酐的可能机制，其中通过磷酰基和羰基氧原子之间与金属离子配位形成七元环中间体。因此，磷酰基的固有性质可能是导致这种迁移的关键因素。
