The Chemistry of <i>C</i>-Glycosides

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Table of contents
  • Contentsv
  • Acknowledgementsxi
  • Abbreviationsxiii
  • Chapter 1. Introduction1
  • 1. Organization of the Book1
  • 1.1 Definition and Nomenclature of C-Glycosides1
  • 1.2 O-Glycosides vs. C-Glycosides: Comparisons of Physical Properties, Anomeric Effects, H-Bonding A4
  • 1.3 Naturally Occurring C-Glycosides7
  • 1.4 C-Glycosides as Stable Pharmacophores10
  • 1.5 Further Reading22
  • 1.6 References22
  • Chapter 2. Electrophilic Substitutions29
  • 2. Introduction29
  • 2.1 Anomeric Activating Groups and Stereoselectivity29
  • 2.2 Cyanation Reactions30
  • 2.3 Alkylation, Allenylation, Allylation and Alkynation Reactions42
  • 2.4 Arylation Reactions71
  • 2.5 Reactions with Enol Ethers, Silylenol Ethers and Enamines89
  • 2.6 Nitroalkylation Reactions98
  • 2.7 Reactions with Allylic Ethers101
  • 2.8 Wittig Reactions with Lactols104
  • 2.9 Nucleophilic Additions to Sugar Lactones Followed by Lactol Reductions111
  • 2.10 Nucleophilic Additions to Sugars Containing Enones116
  • 2.11 Transition Metal Mediated Carbon Monoxide Insertions119
  • 2.12 Reactions Involving Anomeric Carbenes123
  • 2.13 Reactions Involving Exoanomeric Methylenes125
  • 2.14 References128
  • Chapter 3. Nucleophilic Sugar Substitutions133
  • 3. Introduction133
  • 3.1 C1 Lithiated Anomeric Carbanions by Direct Metal Exchange134
  • 3.2 C1 Lithiated Anomeric Carbanions by Reduction140
  • 3.3 C1 Carbanions Stabilized by Sulfones, Sulfides, Sulfoxides, Carboxyl and Nitro Groups143
  • 3.4 References152
  • Chapter 4. Transition Metal Mediated C-Glycosidations155
  • 4. Introduction155
  • 4.1 Direct Coupling of Glycals and Aryl Groups155
  • 4.2 Coupling of Substituted Glycals with Aryl Groups164
  • 4.3 Coupling of Pi-Allyl Complexes of Glycals167
  • 4.4 Mechanistic Considerations171
  • 4.5 References173
  • Chapter 5. Anomeric Radicals175
  • 5. Introduction175
  • 5.1 Sources of Anomeric Radicals and Stereochemical Consequences175
  • 5.2 Anomeric Couplings with Radical Acceptors180
  • 5.3 Intramolecular Radical Reactions192
  • 5.4 References195
  • Chapter 6. Rearrangements and Cycloadditions197
  • 6. Introduction197
  • 6.1 Rearrangements by Substituent Cleavage and Recombination198
  • 6.2 Electrocyclic Rearrangements Involving Glycals201
  • 6.3 Rearrangements from the 2-Hydroxyl Group204
  • 6.4 Bimolecular Cycloadditions206
  • 6.5 Manipulations of C-Glycosides206
  • 6.6 References210
  • Chapter 7. Sugar Ring Formations211
  • 7. Introduction211
  • 7.1 Wittig Reactions of Lactols Followed by Ring Closures212
  • 7.2 Addition of Grignard and Organozinc Reagents to Lactols219
  • 7.3 Cyclization of Suitably Substituted Polyols220
  • 7.4 Rearrangements226
  • 7.5 Cycloadditions230
  • 7.6 Other Methods for the Formation of Sugar Rings233
  • 7.7 References234
  • Chapter 8. Syntheses of C-Di and Trisaccharides237
  • 8. Introduction237
  • 8.1 Syntheses Reported in 1983237
  • 8.2 Syntheses Reported in 1984238
  • 8.3 Syntheses Reported in 1985240
  • 8.4 Syntheses Reported in 1986242
  • 8.5 Syntheses Reported in 1987244
  • 8.6 Syntheses Reported in 1988245
  • 8.7 Syntheses Reported in 1989247
  • 8.8 Syntheses Reported in 1990252
  • 8.9 Syntheses Reported in 1991254
  • 8.10 Syntheses Reported in 1992259
  • 8.11 Syntheses Reported in 1993266
  • 8.12 Syntheses Reported in 1994272
  • 8.13 Trends of the Future274
  • 8.14 References276
  • Index279
  • Authors' Biographies291
Book details
  • Vendor Elsevier S & T
  • SKU 9780080420806
  • ISBN-13 9780080529011

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In recent years C-glycoside chemistry has been one of the main topics in carbohydrate chemistry, not only because of the synthetic challenges posed, but also because C-glycosides have the potential to serve as carbohydrate analogues resistant to metabolic processes. Consequently, this class of compounds is currently receiving much interest as a potential source of therapeutic agents for clinical use. This book provides a broad coverage of the various synthetic methods available for the preparation of C-glycosides, and illustrates the interesting breadth of connections between carbohydrate chemistry and modern general synthetic organic chemistry by including topics such as transition-metal catalysis, radical chemistry, cycloaddition and rearrangement processes. In addition, in the final chapter of the book, the syntheses of C-di and trisaccharides reported through 1994 are reviewed. This well organised account of the synthetic chemistry in this field will prove to be very valuable to a wide range of researchers and advanced students, both as an introduction to the topic and for reference.