Marco Brito-Arias
Biotechnology Unit
National Polytechnic Institute of Mexico (UPIBI-IPN)
Library of Congress Control Number: 2006927420
ISBN 10: 0-387-26251-2
ISBN 13: 978-0-387-26251-2
2007 Springer Science+Business Media, LLC
CONTENTS
1. Glycosides, Synthesis, and Characterization
1.1. Introduction
1.2. Reactions of Monosaccharides
1.3. Chemical Modifications
1.3.1. Oxidations
1.3.2. Periodate Oxidation
1.3.3. Tollens Reaction
1.3.4. Benedict and Fehling Test
1.3.5. Nucleophilic Addition
1.3.6. Enediol Rearrangement
1.3.7. KilianiFischer Synthesis
1.3.8. The Ruff Degradation
1.3.9. Conversion of Pentose to Furfural
1.4. Biosynthesis of Sugars
1.4.1. Sugars as Energy Sources
1.5. Synthesis of Carbohydrates
1.5.1. Chemical Synthesis
1.5.2. C-Glycosyl Amino Acids
1.5.3. Enzymatic Synthesis
1.5.4. Chemoenzymatic Synthesis
1.6. Synthesis of Carbohydrates Mimetics
1.6.1. Iminosugars
1.6.2. Aminosugars
1.6.3. Thiopyranoside Monosaccharides
1.6.4. Carbapyranoside-Saccharides
1.7. Glycoside Reactivity
1.8. The Leaving Groups
1.9. Glycosyl Donors
1.10. Protecting Groups
1.11. Selective Protections
1.12. Selective Deprotections
References
2. O-Glycoside Formation
2.1. General Methods
2.1.1. The Michael Reaction
2.1.2. The Fischer Reaction
2.1.3. The Koenigs-Knorr Reaction
2.1.4. The Helferich Reaction
2.1.5. The Fusion Reaction
2.1.6. The Imidate Reaction
2.1.7. The Sulfur Reaction
2.1.8. The Armed-Disarmed Method
2.1.9. The Glycal Reaction
2.1.10. Miscellaneous Leaving Groups
2.1.10.1 Fluoride Glycosyl Donors
2.1.10.2 Silyl Glycosyl Donors
2.1.10.3 Heterogenous Catalysis
2.1.10.4 The Pool Strategy
2.1.10.5 Phosphate Glycosyl Donors
2.1.11. Enzymatic Approach
2.1.11.1 Enzymatic Synthesis of Oligosaccharides
2.1.12. The Solid-Phase Methodology
2.2. Cyclic Oligosaccharides
2.2.1. Chemoenzymatic and Enzymatic Synthesis
References
3. N-Glycosides
3.1. Nucleoside Formation
3.2. Protecting Groups
3.2.1. Ribofuranoside Protecting Groups
3.3. General Methods
3.3.1. The Michael Reaction
3.3.1.1 General Figure and Conditions
3.3.2. The Fischer-Helferich Reaction
3.3.2.1 General Figure and Conditions
3.3.3. The Davol-Lowy Reaction
3.3.3.1 General Figure and Conditions
3.3.4. Silyl Coupling Reaction
3.3.4.1 General Figure and Conditions
3.3.5. Sulfur-mediated Reaction
3.3.5.1 General Figure and Conditions
3.3.6. Mitsunobu Reaction
3.3.7. Palladium-mediated Reaction
3.3.8. Microbial/Enzymatic Approach
3.4. Oligonucleotide Synthesis
3.4.1. Phosphoramidite Method
3.4.2. Phosphonate Method
3.4.3. Modified Oligonucleotides References
4. Nucleoside Mimetics
4.1. Modified Nucleosides
4.1.1. Heterocycle Modifications
4.1.1.1 C-5 Substituted Pyrimidines
4.1.1.2 C-6 Substituted Pyrimidines
4.1.1.3 Purine Formation
4.1.2. Sugar Modifications
4.1.2.1 23-Dideoxysugars
4.1.2.2 2Deoxynucleosides..........................................190
4.1.2.3 3-Deoxynucleosides........................................192
4.1.2.4 4-Substituted Nucleosides............................. 193
4.1.3. Complex Nucleosides ......................................... 195
4.1.3.1 Fused Heterocyclic Nucleosides...................... 199
4.2. C-Nucleosides ......................................................... 200
4.3. Carbocyclic Nucleosides ........................................ 209
4.3.1. Cyclopropane Carbocyclic Nucleosides ............ 211
4.3.2. Cyclobutane Carbocyclic Nucleosides ............... 212
4.3.3. Cyclopentane Carbocyclic Nucleosides.............. 212
4.3.4. Palladium Mediated............................................... 214
4.3.5. Enzymatic Synthesis............................................... 220
4.3.5.1 Base Ring Formation .......................................... 220
4.3.6. Carbocyclic C-Nucleosides.................................... 223
4.4. Acyclic Nucleosides.................................................... 223
4.5. Thionucleosides ......................................................... 228
4.5.1. Preparation of Thioribofuranosyl Intermediates.... 230
4.5.2. Glycosidic Bond Formation..................................... 236
4.5.3. Chloromercuration Promoted Coupling Reactions 237
4.5.3.1 Silylmediated Coupling Reactions ....................... 237
References .......................................................................... 241
5. C-Glycosides................................................................... 247
5.1. Synthetic Approaches for the Preparation of C-Glycosides......... 247
5.1.1. Electrophilic Glycosyl Donors................................... 250
5.1.1.1 Glycosyl Donors Bearing Good Leaving Groups. 250
5.1.1.2 Other Electrophilic Glycosyl Donors...................... 251
5.1.2. Concerted Reaction and Ring Formation .............. 255
5.1.3. Palladium-Mediated Reactions .............................. 256
5.1.4. Mitsunobu Reaction ................................................. 256
5.1.5. Nucleophilic Sugars ................................................. 257
5.1.6. Cross-Metathesis Reaction .................................... 260
5.1.7. Samarium Promoted Reaction .............................. 260
5.1.8. The Ramberg-B¨acklund Reaction....................... 262
5.1.9. Free Radical Approach............................................ 263
5.1.10. Exoglycals............................................................... 265
5.1.11. The Tether Approach ............................................ 267
References.......................................................................... 270
6. Glycoconjugates............................................................. 272
6.1. Biological Function and Structural Information......... 272
6.1.1. Classification of Glycocoproteins ......................... 273
6.1.2. Recognition Sites.................................................... 275
6.1.3. Structural Information of Glycoproteins.................. 276
6.2. Carbohydrate Binding Proteins ................................ 277
6.2.1. Combining Sites....................................................... 279
6.3. Glycopeptide Synthesis ............................................. 281
6.4. Glycoprotein Synthesis............................................... 285
6.4.1. Indiscriminate Glycosylation ................................... 286
6.4.2. Chemoselective and Site-Specific Glycosylation..289
6.4.3. Site-Selective Glycosylation ................................... 289
6.4.4. Enzymatic Synthesis................................................. 289
6.5. Synthesis of Antigenic Glycoconjugates.................... 292
References............................................................................ 301
7. Hydrolysis of Glycosides ................................................ 304
7.1. Acidic Hydrolysis ......................................................... 304
7.2. Basic Hydrolysis........................................................... 306
7.2.1. Phenolic Glycosides ................................................ 306
7.2.2. Enolic Glycosides ..................................................... 306
7.2.3. β-Susbstituted Alcohol Glycosides.......................... 306
7.3. Enzymatic Hydrolysis ................................................... 308
7.3.1. β-Glucosidases ......................................................... 308
7.3.2. β-Glucanasas, β-Quitinases..................................... 308
7.3.3. β-Cellulase ................................................................ 308
7.3.4. β-Glucuronidase ....................................................... 308
7.3.5. Glycosidase Enzymatic Activity Detection............. 309
7.3.6. Regarding β-1,4-Glucanases (EG)......................... 309
7.3.7. Fluorescent O-Glycosides........................................ 310
7.3.8. O-Glycosides Measured by Absorption ................. 311
7.3.9. Histochemical O-Glycosides ................................... 311
References............................................................................ 313
8. Nuclear Magnetic Resonance of Glycosides ............... 314
8.1. NMR of O-Glycosides .................................................. 314
8.2. N-Glycosides................................................................. 325
References............................................................................ 328
9. X-Ray Diffraction of Glycosides ..................................... 330
9.1. X-Ray Diffraction of O-Glycosides.............................. 331
9.2. X-Ray Diffraction of Nucleosides................................ 337
References............................................................................ 340
10. Mass Spectrometry of Glycosides .............................. 342
References............................................................................ 348
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