Functionalization of glucose at position C-3 for transition metal coordination: organo-rhenium complexes with carbohydrate skeletons.
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)](2)[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.
Dumas
Cécile
C
Center for Radiopharmaceutical Science of the ETH-PSI-USZ, Paul Scherrer Institute, CH-5232 Villigen, Switzerland.
Petrig
Jeannine
J
Frei
Luzia
L
Spingler
Bernhard
B
Schibli
Roger
R
D002241:Carbohydrates / Q000737:chemistry; D002614:Chelating Agents / Q000737:chemistry; D005947:Glucose / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013057:Spectrum Analysis; D028561:Transition Elements / Q000737:chemistry*
D002241:Carbohydrates; D002614:Chelating Agents; D009942:Organometallic Compounds; D028561:Transition Elements; D005947:Glucose