Nitrogen-containing carbohydrate derivatives. XIV. Configurational studies on amino-sugars using cuprammonium solutions.
A study has been made of the optical rotational shifts and conductance changes in cuprammonium solutions of eight isomeric amino-glycosides. The results are in agreement with the findings of Reeves for vicinal diol systems. Care must be taken in using small optical rotational shifts alone as evidence for the absence of complexing with a vic-amino-alcohol grouping. These techniques have been used to relate methyl 5-amino-1,3-O-benzylidene-5-deoxy-β-D-fructoside and -α-L-sorboside to their respective hydroxy-compounds.
Copper(II) complexes of aminocarbohydrate beta-ketoenaminic ligands: efficient catalysts in catechol oxidation.
Copper(II) complexes of tridentate dianionic beta-ketoenaminic ligands derived from differently functionalized amino-deoxyglucoses were synthesized and characterized with respect to their structural, spectroscopic, and catalytic properties. The (probably dimeric) complex [1,2-O-isopropylidene-6-N-(3-acetyl-2-oxobut-3-enyl)amino-6-deoxyglucofuranoso)copper(II) Cu(3a) was a highly efficient catalyst for the catechol-oxidase-like oxidation of 3,5-di-tert-butylcatechol (dtbc) into 3,5-ditert-butylquinone (dtbq) by molecular oxygen (kcat=2.63s(-1)). In contrast to this magnetically "normal" complex Cu(3a), the analogous dinuclear complex [[Cu(2a)]2], derived from the isomeric amino sugar 5-amino-5-deoxyglucofuranose, forms six-membered chelate rings with the sugar moiety and has very strong antiferromagnetic-coupled copper atoms (resulting in a diamagnetic ground state). It has a rather insignificant activity (kcat < 10(-3)s(-1)). The ligand H2 1a, derived from a (protected) 6-amino-6-deoxyglucopyranose, forms a trinuclear complex [[Cu(1a)]]2.Cu(OAc)2] in which two basic formula units are bridged by one copper acetate. This compound and the complex derived from an (isomeric) aminodeoxyglucopyranose ([Cu(4a)]: kcat approximately equals 0.03 s(-1)) show moderate activity. All complexes with a peripheral ethoxycarbonyl group instead of the acetyl substituent R2, Cu(1b)-Cu(3b) and Cu(4c), are inactive. The complexes derived from 2-hydroxocyclohexylamine, Cu(5a) and Cu(5c), which were used as models of the active complex Cu(3a), have the typical "cubane-like" tetranuclear structure known from many copper complexes with derivatives of saturated 2-aminoalcohols. They are inactive with respect to the activation of dioxygen.
Synthesis of 2,4-dideoxy-.beta.-D-erythro-hexopyranosyl nucleosides
The synthesis of 1-(2,4-dideoxy-β-D-erythro-hexopyranosyl)thymine (12) 1 was accomplished using two different synthetic routes. It was obtained starting either from 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose or from tri-O-acetyl-D-glucal. The other modified nucleosides, with either a cytosine, guanine, or adenine moiety, were synthesized using the second reaction scheme. Deoxygenation reactions were accomplished with the (2,4-dichlorophenoxy)thiocarbonyl derivatives generated in situ