Quantifying the Electronic Effects of Carbohydrate Hydroxy Groups by Using Aminosugar Models

TY - JOUR

T1 - Quantifying the Electronic Effects of Carbohydrate Hydroxy Groups by Using Aminosugar Models

AU - Pedersen, Christian Marcus

AU - Olsen, Jacob

AU - Brka, Azra

AU - Bols, Mikael

PY - 2011/6/14

Y1 - 2011/6/14

N2 - 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 pKa 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-NH2>3-NH2>2-NH2>4-NH2 (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.

AB - 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 pKa 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-NH2>3-NH2>2-NH2>4-NH2 (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.

M3 - Journal article

SN - 0947-6539

VL - 17

SP - 7080

EP - 7086

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

IS - 25

ER -