| Preface | ix |
| Guy Gordon Studdy Dutton, 1923-1997 | |
| Text | 1 |
| Iodine in Carbohydrate Chemistry | |
| I. | Introduction | 9 |
| II. | Glycosylation | 10 |
| 1. | Uses of Iodine | 10 |
| 2. | Glycosyl Iodides | 10 |
| 3. | Activation of n-Pentenyl Glycosides | 13 |
| 4. | Activation of Thioglycosides | 15 |
| III. | Activation of Glycals | 19 |
| IV. | Pseudohalogens | 26 |
| V. | Hypervalent Iodine | 30 |
| 1. | Dess-Martin Reagent | 36 |
| VI. | Reactions Involving Phosphorus | 38 |
| 1. | Rydon Reagents | 38 |
| 2. | The Garegg-Samuelsson Reagent | 39 |
| VII. | Installation and Removal of Protecting Groups Using Iodine | 44 |
| VIII. | Iodocyclizations | 50 |
| IX. | Miscellaneous Reactions | 55 |
| References | 57 |
| Structure of Anomeric Glycosyl Radicals and Their Transformations under Reductive Conditions | |
| I. | Introduction | 65 |
| II. | Structure of Sugar-Derived Radicals | 67 |
| 1. | Structure of Carbon-Centered Acetal Radicals | 68 |
| 2. | ESR Studies of Carbohydrate-Derived Radicals | 69 |
| 3. | Interpretation in the Framework of the Frontier Molecular Orbital (FMO) Theory | 85 |
| III. | Radical Methods to Anhydroalditols from Glycosyl Derivatives | 86 |
| 1. | Radical Reduction with Tin and Silicon Hydrides | 87 |
| 2. | Synthesis of Anhydroalditols by Single-Electron Transfer | 100 |
| 3. | Synthesis of Ring-Fused and C-Branched Anhydroalditols | 102 |
| 4. | Stereoselectivity of Hydrogen-Atom Transfer at Anomeric Radicals | 103 |
| IV. | Diastereoselective Reductions of Substituted Anomeric Radicals | 106 |
| 1. | Stereocontrolled Synthesis of O-Glycosides and Analogs | 107 |
| 2. | Stereocontrolled Synthesis of C-Glycosyl Compounds and Analogues | 115 |
| 3. | Radical Routes to Nucleosides | 127 |
| 4. | Reduction Diastereoselectivity of Substituted Anomeric Radicals | 129 |
| V. | Synthesis of 2-Deoxy Sugars by Radical-Induced Rearrangement | 130 |
| 1. | Synthesis of 2-Deoxy Sugars by 2,1-Acyloxy Group Rearrangements | 131 |
| 2. | Synthesis of 2-Deoxy Sugars by 2,1-Phosphonyloxy Group Rearrangement | 135 |
| 3. | Mechanism of Radical-Induced 2,1-Migrations of Ester Groups | 138 |
| VI. | Radical-Mediated Eliminations: Formation of Glycals | 139 |
| VII. | Conclusion | 142 |
| References | 143 |
| Oligosaccharide-Protein Conjugates as Vaccine Candidates against Bacteria | |
| I. | Overview of Polysaccharide-Based Antibacterial Vaccines | 153 |
| II. | Synthesis and Immunological Evaluation of Protein Conjugates of Oligosaccharide Components of Bacterial Polysaccharides | 157 |
| 1. | Studies on Dextran-Related Oligosaccharide-Protein Conjugates | 157 |
| 2. | Protein Conjugates of Oligosaccharide Fragments of Capsular Polysaccharides | 161 |
| 3. | Protein Conjugates of Oligosaccharides Related to Lipopolysaccharides | 179 |
| III. | Conclusion | 193 |
| References | 194 |
| Molecular Structure of the Carbohydrate-Protein Linkage Region Fragments from Connective-Tissue Proteoglycans | |
| I. | Introduction | 201 |
| II. | Isolation of Linkage-Region Oligosaccharides | 205 |
| III. | Identification of Carbohydrate Spin Systems | 206 |
| IV. | Identification of the Peptide Spin Systems | 209 |
| V. | Conformational Analysis of the Interglycosidic Linkages | 210 |
| VI. | Conformation of the Glycopeptide Linkage | 211 |
| VII. | Influence of Glycosylation on Proteoglycan Core-Peptide Backbone Conformation | 213 |
| VIII. | Structural Studies on the Carbohydrate-Protein Linkage Region | 215 |
| 1. | Dermatan Sulfate | 215 |
| 2. | Chondroitin Sulfate | 216 |
| 3. | Heparan Sulfate | 219 |
| 4. | Heparin | 223 |
| IX. | NMR Spectral Properties of Linkage-Region Oligosaccharides | 224 |
| X. | Biosynthesis of Carbohydrate-Protein Linkage-Region Oligosaccharides | 228 |
| References | 229 |
| The Conformation of C-Glycosyl Compounds | |
| I. | Introduction | 235 |
| II. | Nomenclature | 236 |
| III. | C-Glycosyl Compounds in Chemistry and Biochemistry | 237 |
| IV. | Conformation of Saccharides: An Overview on the Relative Role of the Exoanomeric Effect and Steric Interactions | 239 |
| V. | The Use of NMR and Molecular Modeling as Tools in Conformational Analysis of C-Glycosyl Compounds in Solution | 243 |
| VI. | Conformation of C-Glycosyl Compounds | 246 |
| 1. | Conformation in the Solid State | 246 |
| 2. | Conformation in Solution | 247 |
| VII. | Conclusions | 279 |
| References | 280 |
| Author Index | 285 |
| Subject Index | 311 |
