Versatile routes to C-2- and C-6-functionalized glucose derivatives of iminodiacetic acid.
A series of novel d-glucose derivatives, functionalized at the C-2 or the C-6 position with an iminodiacetic acid moiety for transition-metal complexation, has been prepared. The sugar and the metal-chelating parts are separated by either propyl or octyl chains and were introduced by the reaction of bromoalkylamine. Either N-1-Boc-3-bromopropylamine (17) or N-(8-bromooctyl)phthalimide (19) reacted with methyl 3,5,6-tri-O-benzyl-alpha-beta-d-glucofuranoside (4) (C-2 position) and 1,2:3,5-(O-methylene)-alpha-d-glucose (11) (C-6 position), respectively, in the presence of sodium hydride in DMF at room temperature, affording the desired intermediates. For aminopropyl derivatives, yields varied between 57% and 65%, and for aminooctyl derivatives, yields varied between 40% and 71%. After deprotection of the amine functionality, the metal chelate was built up by dialkylation (6a-c and 13a,b) with methyl bromoacetate in the presence of triethylamine under reflux in THF. Yields varied between 56% and 69% for the glucose modified at the C-2 position and between 58% and 62% for the one modified at the C-6 position. All compounds were characterized by 1H or 13C NMR or both, IR, and mass spectroscopy. Final products were isolated as a mixture of alpha and beta anomers.
Dumas
Cécile
C
Center for Radiopharmaceutical Science of the ETH, PSI, USZ, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland.
Schibli
Roger
R
Schubiger
P August
PA
D020650:Combinatorial Chemistry Techniques; D005947:Glucose / Q000031:analogs & derivatives* / Q000138:chemical synthesis*; D007098:Imino Acids / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013237:Stereoisomerism
D007098:Imino Acids; D007202:Indicators and Reagents; D005947:Glucose; C008109:iminodiacetic acid