Bibliographic record and links to related information available from the Library of Congress catalog
Note: Electronic data is machine generated. May be incomplete or contain other coding.
1. Glycosides, Synthesis, and Characterization ..... ......................... 1 1.1. Introduction................................................................. 1 1.2. Reactions of Monosaccharides......................................... 2 1.3. Chemical Modifications ........ ............................................. 2 1.3.1. Oxidations .......................................................... 3 1.3.2. Periodate Oxidation........................................... 4 1.3.3. Tollens Reaction.................................................. 5 1.3.4. Benedict and Fehling Test ...................................... 5 1.3.5. Nucleophilic Addition.......................................... 6 1.3.6. Enediol Rearrangement ........................................... 9 1.3.7. KilianiFischer Synthesis ........................................... 9 1.3.8. The Ruff Degradation .......................................... 10 1.3.9. Conversion of Pentose to Furfural.............................. 10 1.4. Biosynthesis of Sugars.................................................... 11 1.4.1. Sugars as Energy Sources....................................... 11 1.5. Synthesis of Carbohydrates............................. ........... ......... 12 1.5.1. Chemical Synthesis.............................................. 12 1.5.2. C-Glycosyl Amino Acids...................................... 16 1.5.3. Enzymatic Synthesis............................................ 21 1.5.4. Chemoenzymatic Synthesis .................................... 23 1.6. Synthesis of Carbohydrates Mimetics...... ............................... 25 1.6.1. Iminosugars ........................................................ 25 1.6.2. Aminosugars ......... ............................................ . 29 1.6.3. Thiopyranoside Monosaccharides........................... 34 1.6.4. Carbapyranoside-Saccharides................................. 34 1.7. Glycoside Reactivity....................................................... 35 1.8. The Leaving Groups...................................................... 35 1.9. Glycosyl Donors .......................................................... 39 1.10. Protecting Groups......................................................... 43 1.11. Selective Protections .................................. ......... ....... 52 1.12. Selective Deprotections................................................... 59 References .............................. ............................................. 63 2. O-Glycoside Formation ....................................................... 68 2.1. General M ethods.......................................................... 68 2.1.1. The M ichael Reaction........ ............. .. .............. 68 2.1.2. The Fischer Reaction......................................... 70 2.1.3. The Koenigs-Knorr Reaction ................................ 73 2.1.4. The Helferich Reaction .................................... 76 2.1.5. The Fusion Reaction........................................... 78 2.1.6. The Imidate Reaction........................................ 80 2.1.7. The Sulfur Reaction ......................................... 88 2.1.8. The Armed-Disarmed Method ............................... 95 2.1.9. The Glycal Reaction....................................... 98 2.1.10. Miscellaneous Leaving Groups............................. .... 104 2.1.10.1 Fluoride Glycosyl Donors ........................ 104 2.1.10.2 Silyl Glycosyl Donors............................. 105 2.1.10.3 Heterogenous Catalysis ......................... .. 110 2.1.10.4 The Pool Strategy.................................... 112 2.1.10.5 Phosphate Glycosyl Donors...................... 112 2.1.11. Enzymatic Approach........................................ 113 2.1.11.1 Enzymatic Synthesis of Oligosaccharides ...... 117 2.1.12. The Solid-Phase Methodology .............................. 117 2.2. Cyclic Oligosaccharides................................................. 124 2.2.1. Chemoenzymatic and Enzymatic Synthesis................ 127 R eferences .... ........ ................. ................... .................... ... 134 3. N-Glycosides.................................................................... 138 3.1. Nucleoside Formation.... ............................................. 139 3.2. Protecting Groups .............. ............................. ......... . 140 3.2.1. Ribofuranoside Protecting Groups........................ 142 3.3. General Methods............................................... ...... 151 3.3.1. The M ichael Reaction......................... ................. 153 3.3.1.1 General Figure and Conditions ................... 153 3.3.2. The Fischer-Helferich Reaction........................... ... 156 3.3.2.1 General Figure and Conditions .................. 156 3.3.3. The Davol-Lowy Reaction........ ............................. 157 3.3.3.1 General Figure and Conditions ................... 157 3.3.4. Silyl Coupling Reaction....................................... 159 3.3.4.1 General Figure and Conditions ................... 159 3.3.5. Sulfur-mediated Reaction................. .... . ....... 163 3.3.5.1 General Figure and Conditions ................... 163 3.3.6. Mitsunobu Reaction ........................................ 163 3.3.7. Palladium-mediated Reaction................................. 164 3.3.8. Microbial/Enzymatic Approach............................. 166 3.4. Oligonucleotide Synthesis............................. ... ..... ...... 167 3.4.1. Phosphoramidite Method............ ..... ......... ...... 170 3.4.2. Phosphonate Method................................................ 172 3.4.3. Modified Oligonucleotides .................................... 172 R eferences ........................................................................ 176 4. Nucleoside Mimetics ............................................................ 179 4.1. M odified Nucleosides..................................................... 180 4.1.1. Heterocycle Modifications.................................. 181 4.1.1.1 C-5 Substituted Pyrimidines...................... 181 4.1.1.2 C-6 Substituted Pyrimidines .... ............ 183 4.1.1.3 Purine Formation................................. 184 4.1.2. Sugar Modifications......................................... 185 4.1.2.1 2'3'-Dideoxysugars................................. 185 4.1.2.2 2'Deoxynucleosides............................... 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-N ucleosides............................................................. 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-Baicklund Reaction............................ 262 5.1.9. Free Radical Approach........................................ 263 5.1.10. Exoglycals............. .................... ................. 265 5.111. The Tether Approach ................... ..................... 267 R eferences........................................................................ 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. 3-Susbstituted Alcohol Glycosides........................ 306 7.3. Enzymatic Hydrolysis......................................... ..... 308 7.3.1. 3-Glucosidases............................................. 308 7.3.2. (-Glucanasas, P-Quitinases................................. 308 7.3.3. P-Cellulase....... ............. .............................. 308 7.3.4. -Glucuronidase ................................... ...... 308 7.3.5. Glycosidase Enzymatic Activity-Detection............... 309 7.3.6. Regarding 3-1,4-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 R eferences........................................................................ 313 8. Nuclear Magnetic Resonance of Glycosides .............................. 314 8.1. NMR of O-Glycosides ................................................ 314 8.2. N-Glycosides ................................ .......................... 325 R eferences .......................................................................... 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 R eferences .......................................................................... 340 10. Mass Spectrometry of Glycosides ................. ........................ 342 R eferences .......................................................................... 348