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Quantifying the Electronic Effects of Carbohydrate Hydroxy Groups by Using Aminosugar Models
Author(s) -
Pedersen Christian M.,
Olsen Jacob,
Brka Azra B.,
Bols Mikael
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201100020
Subject(s) - chemistry , carbohydrate , anomer , amine gas treating , stereochemistry , sugar , oxygen atom , regioselectivity , aminosugar , medicinal chemistry , organic chemistry , molecule , catalysis , glucosamine
Methyl amino‐deoxy‐glycosides with α‐ and β‐gluco, α‐galacto, or α‐manno stereochemistry with the amino functionality in each of the four possible non‐anomeric positions have been synthesized and their p K a values determined by titration. These model compounds were chosen because they are the amino derivatives of the most common glycosyl acceptors. From this study it was possible to evaluate the electron density at each of the given positions in the carbohydrate and compare them. Some general trends were observed: The basicity of the amino groups decreases in the order 6‐NH 2 >3‐NH 2 >2‐NH 2 >4‐NH 2 (referring to the position). The basicity of a of an amino‐deoxy‐sugar generally increases when one or more substituents on the sugar ring are axial. The basicity decreases when the amine is antiperiplanar to an oxygen atom. These findings are in agreement with the observations obtained from glycosylation chemistry and the regioselective protection of sugars.