Carbohydrates (eBook)

Foreword 6
Preface 7
Contents 9
Introduction 14
Stereochemistry 15
Representation of Monosaccharides 15
The Nomenclature of Carbohydrates 22
References 38
Conformational Analysis of Monosaccharides 39
Conformational Analysis of Acyclic Hydrocarbons 40
Conformational Analysis of Acyclic (Aldehydo) Forms of Monosaccharides 43
Conformational Analysis of Cyclic (Lactol, Hemiacetal) Forms of Monosaccharides 45
Calculation of Conformational Energies of Pyranoses 53
References 65
Anomeric Effect 69
References 100
Isomerization of Sugars 106
Mutarotation 106
Anomerization 116
Lobry de Bruyn–Alberda van Ekenstein Transformation 119
References 120
Relative Reactivity of Hydroxyl Groups in Monosaccharides 123
Introduction 123
Selective Acylation (Esterification) 124
Selective Alkylation and/or Arylation of Glycopyranosides 146
References 149
Cyclic Acetals and Ketals 153
Acetalation 158
Ketalation 160
Transacetalation and Transketalation 162
The Isomerization of Cyclic Acetals and Ketals 164
Removal of Acetal and Ketal Groups 167
References 173
Nucleophilic Displacement and the Neighboring Group Participation 178
Nucleophilic Displacement 178
Nucleophilic Displacements with Neighboring Group Participation 188
References 197
Anhydrosugars 200
1,6-Anhydrosugars (Glycosanes) 200
1,4-Anhydrosugars 207
1,2-Anhydrosugars (Brigl’s Anhydrides) 209
Anhydrosugars Not Involving the Anomeric Carbon 212
Rearrangements of Anhydrosugars 220
References 223
Amino Sugars 229
Ammonolysis of Oxiranes 229
Nucleophilic Displacement of Sulfonates (or Halides) with Nitrogen Nucleophiles 234
Glycosylamines and N-Glycosides 239
Acid-Catalyzed Hydrolysis of Purine and Pyrimidine Nucleosides 245
References 248
Oxidation of Monosaccharides 253
Selective Oxidations of Monosaccharides 253
Nonselective Oxidation of Secondary Hydroxyl Groups 256
DMSO–DCC Method (Pfitzner–Moffatt Oxidation) 263
DMSO–Acetic Anhydride Method 266
DMSO–Phosphorus Pentoxide 271
DMSO–Sulfurtrioxide Pyridine (“Parikh–Doering” Oxidation) 272
Chromium Trioxide Oxidation 274
Chromium Trioxide–Pyridine Oxidation 274
Chromium Trioxide–Acetic Acid 278
Pyridinium Chlorochromate 278
Nicotine Dichromate 280
Pyridinium Dichromate–Acetic Anhydride 280
Oxidation of Carbohydrates with the Cleavage of Carbohydrate Chain 281
References 292
Addition of Nucleophiles to Glycopyranosiduloses 299
The Addition of a Hydride Ion (Reduction) 299
The Addition of Carbon Nucleophiles: Synthesis of Branched Chain Sugars 305
Synthesis of Branched Chain Sugars with Functionalized Branched Chain 316
References 326
Chemistry of the Glycosidic Bond 330
Introduction 330
Glycoside Synthesis 331
Cleavage of Glycosidic Bonds 381
References 413
Synthesis of Polychiral Natural Products from Carbohydrates 429
Macrolide Antibiotics: Erythronolides A and B 429
Thromboxane B2 444
Swainsonine 447
Biotin 449
Pseudomonic Acid C 451
Aplasmomycin 462
References 468
Carbohydrate-Based Antibiotics 474
Aminoglycoside Antibiotics 474
References 487
Higher-Carbon Monosaccharides 492
Introduction 492
Synthesis of Higher-Carbon Sugars 495
References 517
Author Index 522
Subject Index 543