Dumas Cécile, Petrig Jeannine, Frei Luzia, Spingler Bernhard, Schibli Roger
Center for Radiopharmaceutical Science of the ETH-PSI-USZ, Paul Scherrer Institute, CH-5232 Villigen, Switzerland.
Bioconjug Chem. 2005 Mar-Apr;16(2):421-8. doi: 10.1021/bc049744i.
Novel 3-O-[1,2;5,6-di-O-isopropylidene-alpha-D-glucofuranose] and 3-O-[D-glucose] derivatives with an iminodiacetate (N,O,O), a histidinate, and an N-(acetetyl)picolylamine (N,N,O) chelating system for tridentate coordination of the organometallic M(CO)(3)-fragment (M = Tc, Re) have been prepared. The chelates were introduced and assembled through reductive amination starting from 3-O-[1,2;5,6-di-O-isopropylidene-alpha-D-glucofuranose]-acetaldehyde. After deprotection, the pyranose derivatives were reacted with the precursor NEt(4)[ReBr(3)(CO)(3)] to afford the corresponding organometallic complexes in yields between 54% and 94%. The NMR, MS, and IR analyses corroborated the tridentate coordination of the organometallic metal center exclusively via the synthetic chelates. In the case of the N-(acetyl)picolylamine derivative, the coordinative properties were further confirmed by X-ray structure analysis of the first Re(CO)(3)-D-glucofuranose complex. All glucose complexes unveiled good stability and solubility in organic and aqueous media.
已制备出具有亚氨基二乙酸（N,O,O）、组氨酸盐和N-（乙酰基）吡啶甲胺（N,N,O）螯合体系的新型3-O-[1,2;5,6-二-O-亚异丙基-α-D-吡喃葡萄糖]和3-O-[D-葡萄糖]衍生物，用于三齿配位有机金属M(CO)(3)-片段（M = Tc，Re）。螯合物通过从3-O-[1,2;5,6-二-O-亚异丙基-α-D-吡喃葡萄糖]-乙醛开始的还原胺化反应引入并组装。脱保护后，吡喃糖衍生物与前体NEt(4)[ReBr(3)(CO)(3)]反应，以54%至94%的产率得到相应的有机金属配合物。NMR、MS和IR分析证实了有机金属金属中心仅通过合成螯合物进行三齿配位。对于N-（乙酰基）吡啶甲胺衍生物，通过首个Re(CO)(3)-D-吡喃葡萄糖配合物的X射线结构分析进一步证实了其配位性质。所有葡萄糖配合物在有机和水性介质中均表现出良好的稳定性和溶解性。
