Abbreviations
1. Introduction ................................................. l
2. Structure of saccharides ..................................... 5
2.1. Structure of monosaccharides ............................ 5
2.2. Structure of simple oligosaccharides ................... 28
2.3. Structure of polysaccharides ........................... 34
2.4. Conformational analysis of saccharides ................. 43
Exercises and problems ...................................... 49
3. Protecting groups for carbohydrates ......................... 53
3.1. Protection of the anomeric center ...................... 54
3.2. Acyl protecting groups ................................. 61
3.3. Ether protecting groups ................................ 70
3.4. Acetal protecting groups ............................... 78
3.5. Orthoesters as protecting groups ....................... 91
3.6. TV-Protection for amino sugars ......................... 93
3.7. Enymes in protecting group chemistry ................... 97
3.8. Carbohydrate scaffolds and orthogonality of
protecting groups ...................................... 98
3.9. Protecting group patterns for allyl α-D-mannosides .... 101
Exercises and problems ..................................... 104
4. Important modifications and functionalizations
of the sugar ring .......................................... 107
4.1. Activation-substitution reactions at the
carbohydrate ring ..................................... 108
4.2. Deoxyhalo derivatives ................................. 112
4.3. Synthesis and reactions of anhydro sugars ............. 117
4.4. Deoxygenation of carbohydrates ........................ 121
4.5. Functionalization at the anomeric center .............. 127
4.6. Unsaturated saccharides - Glycals ..................... 130
4.7. Epimerizations ........................................ 138
4.8. Carbohydrates as chiral pool materials ................ 143
Exercises and problems ..................................... 154
5. O-Glycoside synthesis ...................................... 157
5.1. 1,2-trans Glycosidation ............................... 160
5.2. 1,2-cis Glycosidation ................................. 162
5.3. Participation of the solvent .......................... 163
5.4. The Koenigs-Knorr method .............................. 166
5.5. The trichloroacetimidate method ....................... 168
5.6. Thioglycosides ........................................ 174
5.7. n-Pentenyl glycosides ................................. 178
5.8. Synthesis of 2-deoxy glycosides ....................... 180
5.9. Synthesis of β-mannopyranosides ....................... 183
5.10.Synthesis of 2-deoxy-2-acetamido-glycopyranosides ..... 188
5.11.Synthesis of glycopeptides ............................ 191
5.12.Solid phase oligosaccharide synthesis ................. 193
5.13.Glycoside synthesis employing enzymes ................. 195
5.14.Glycosylation strategies .............................. 199
Exercises and problems ..................................... 209
6. Structure and biosynthesis of glycoconjugates .............. 213
6.1. Structural diversity of oligosaccharides .............. 213
6.2. Structures of glycoconjugates ......................... 215
6.2.1. Structures of glycoproteins .................... 218
6.2.2. Structures of glycolipids ...................... 224
6.3. Biosynthesis of oligosaccharides ...................... 229
6.4. Biosynthesis of N-glycoproteins ....................... 232
6.5. Biosynthesis of O-glycoproteins ....................... 234
6.6. Biosynthesis of glycosphingolipids .................... 235
Exercises and problems ..................................... 238
7. Glycobiology ............................................... 241
7.1. Blood group specificities ............................. 242
7.2. Lectins ............................................... 243
7.3. Oligosaccharide epitopes critical in cell biology ..... 249
7.4. Understanding of the molecular interactions
of the glycocalyx ..................................... 255
7.5. Carbohydrate microarrays .............................. 256
7.6. Glycomimetics ......................................... 259
7.7. Biochemical engineering ............................... 267
7.8. Microbial adhesion .................................... 271
7.9. Carbohydrate drugs .................................... 275
Exercises and problems ..................................... 284
8. Purification and analysis of carbohydrates ................. 287
8.1. Сhromatography and po1arimetry ........................ 287
8.2. N MR spectroscopy ..................................... 291
8.3. Mass spectrometry ..................................... 300
9. The literature of carbohydrate chemistry ................... 303
List of experimental procedures ............................... 307
List of tables ................................................ 309
Subject index ................................................. 311
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