2.2 Oxidation, Reduction,
and Deoxygenation
Robert Madsen
Department of Chemistry, Center for Sustainable and Green Chemistry,
Technical University of Denmark, Lyngby 2800, Denmark
rm@kemi.dtu.dk
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2
Oxidations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2.1 Oxidation at the Anomeric Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2.2 Oxidation of Primary Alcohols to Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
2.3 Oxidation of Primary Alcohols to Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
2.4 Oxidation of Secondary Alcohols to Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
2.5 Epoxidation, Dihydroxylation, and Azidonitration of Olefins . . . . . . . . . . . . . . . . . . . . . 196
2.6 Bromination at Ring Positions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
3
Reductions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.1 Reduction at the Anomeric Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.2 Reduction of Carboxylic Acids to Primary Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
3.3 Reduction of Ketones to Secondary Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
3.4 Reduction of Oximes to Primary Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
3.5 Hydrogenation of Olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
4
Deoxygenations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
4.1 Deoxygenation at the Anomeric Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
4.2 Deoxygenation of Primary Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
4.3 Deoxygenation of Secondary Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
Abstract
In this chapter, methods for oxidation, reduction, and deoxygenation of carbohydrates are presented. In most cases, the reactions have been used on aldoses and their derivatives including glycosides, uronic acids, glycals, and other unsaturated monosaccharides. A number of
reactions have also been applied to aldonolactones. The methods include both chemical and
enzymatic procedures and some of these can be applied for regioselective transformation of
unprotected or partially protected carbohydrates.
Keywords
Azidonitration; Deoxygenation; Dihydroxylation; Epoxidation; Hydrogenation; Oxidation;
Photobromination; Reduction
In: Glycoscience. Fraser-Reid B, Tatsuta K, Thiem J (eds)
Chapter-DOI 10-1007/978-3-540-30429-6_4: © Springer-Verlag Berlin Heidelberg 2008