Substrate-dependent chemoselective aldose-aldose and aldose-ketose isomerizations of carbohydrates promoted by a combination of calcium ion and monoamines

Epimerization of aldoses at C-2 has been extensively investigated by using various metal ions in conjunction with diamines, monoamines, and aminoalcoh ols. Aldoses are epimerized at C-2 by a combination of alkaline-earth or ra re-earth metal ions (Ca2+, Sr2+, pr(3+), or Ce3+) and such monoamines as tr iethylamine. In particular, the Ca2+-triethylamine system proved effective in promoting aldose-ketose isomerization as well as C-2 epimerization of al doses. C-13 NMR studies using D-(1-C-13)glucose and D-(1-C-13)galactose wit h the CaCl2 system in CD3OD revealed that the C-2 epimerization proceeds vi a stereospecific rearrangement of the carbon skeleton, or 1,2-carbon shift, and ketose formation proceeds partially through an intramolecular hydrogen migration or 1,2-hydride shift and, in part, via an enediol intermediate. These simultaneous aldose-aldose and aldose-ketose isomerizations showed in teresting substrate-dependent chemoselectivity. Whereas the mannose-type al doses having 2,3-erythro configuration (D-mannose, D-lyxose, and D-ribose) showed considerable resistance to both the C-2 epimerization and the aldose -ketose isomerization, the glucose-type sugars having 2,3-threo and 3,4-thr eo configurations, D-glucose and D-xylose, are mainly epimerized at C-2 and those having the 2,3-threo and 3,4-erythro configurations, D-galactose and D-arabinose, were mostly isomerized into 2-ketoses. These features are of potential interest in relevance to biomimic sugar transformations by metal ions. (C) 2001 Elsevier Science Ltd. All rights reserved.