Mechanistic studies of diastereomeric nickel(II) N-glycoside complexes using tandem mass spectrometry

被引:51
作者
Smith, G [1 ]
Leary, JA [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
关键词
D O I
10.1021/ja9814319
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Ni(II) N-glycoside complexes of four diastereomeric monosaccharides were synthesized and analyzed by fast atom bombardment-mass spectrometry. The average kinetic energy release (KER) associated with the formation of a C2H4O2 neutral loss was indicative of stereochemical differences in the coordinated monosaccharide. Isotopic labeling studies and various linked scanning techniques were undertaken, suggesting multiple dissociation pathways from different reacting configurations, leading to the formation of isomeric [M-C2H4O2] product ions. Additionally, computational studies predict the presence of large structural differences between complexes possessing axial or equatorial C-2 substituents.
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页码:13046 / 13056
页数:11
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