Synthesis and Characterization of Glycosides

362 Pages·2006·3.35 MB·English

by  Marco Brito-Arias

Synthesis and Characterization of
Glycosides
Synthesis and Characterization of
Glycosides
Marco Brito-Arias
BiotechnologyUnit
NationalPolytechnicInstituteofMexico(UPIBI-IPN)
MarcoBrito-Arias
BiotechnologyUnit
NationalPolytechnicInstitute,Mexico
laLagunaTicomaˆ
Mexico
LibraryofCongressControlNumber:2006927420
ISBN10:0-387-26251-2
ISBN13:978-0-387-26251-2
(cid:1)C 2007SpringerScience+BusinessMedia,LLC
Allrightsreserved.Thisworkmaynotbetranslatedorcopiedinwholeorinpartwithoutthewritten
permissionofthepublisher(SpringerScience+BusinessMedia,LLC,233SpringStreet,NewYork,
NY10013,USA),exceptforbriefexcerptsinconnectionwithreviewsorscholarlyanalysis.Use
in connection with any form of information storage and retrieval, electronic adaptation, computer
software,orbysimilarordissimilarmethodologynowknownorhereafterdevelopedisforbidden.
Theuseinthispublicationoftradenames,trademarks,servicemarks,andsimilarterms,evenifthey
arenotidentifiedassuch,isnottobetakenasanexpressionofopinionastowhetherornottheyare
subjecttoproprietaryrights.
9 8 7 6 5 4 3 2 1
springer.com
ToCarminaDaniela
Contents
Preface................................................................................... xii
1. Glycosides,Synthesis,andCharacterization............................... 1
1.1. Introduction.................................................................. 1
1.2. ReactionsofMonosaccharides........................................... 2
1.3. ChemicalModifications................................................... 2
1.3.1. Oxidations........................................................... 3
1.3.2. PeriodateOxidation................................................ 4
1.3.3. TollensReaction.................................................... 5
1.3.4. BenedictandFehlingTest........................................ 5
1.3.5. NucleophilicAddition............................................. 6
1.3.6. EnediolRearrangement........................................... 9
1.3.7. KilianiFischerSynthesis.......................................... 9
1.3.8. TheRuffDegradation............................................. 10
1.3.9. ConversionofPentosetoFurfural............................... 10
1.4. BiosynthesisofSugars..................................................... 11
1.4.1. SugarsasEnergySources......................................... 11
1.5. SynthesisofCarbohydrates............................................... 12
1.5.1. ChemicalSynthesis................................................ 12
1.5.2. C-GlycosylAminoAcids......................................... 16
1.5.3. EnzymaticSynthesis............................................... 21
1.5.4. ChemoenzymaticSynthesis...................................... 23
1.6. SynthesisofCarbohydratesMimetics................................... 25
1.6.1. Iminosugars ......................................................... 25
1.6.2. Aminosugars........................................................ 29
1.6.3. ThiopyranosideMonosaccharides............................... 34
1.6.4. Carbapyranoside-Saccharides.................................... 34
1.7. GlycosideReactivity....................................................... 35
1.8. TheLeavingGroups........................................................ 35
1.9. GlycosylDonors............................................................ 39
1.10. ProtectingGroups........................................................... 43
vii
viii Contents
1.11. SelectiveProtections....................................................... 52
1.12. SelectiveDeprotections.................................................... 59
References........................................................................... 63
2. O-GlycosideFormation.......................................................... 68
2.1. GeneralMethods............................................................ 68
2.1.1. TheMichaelReaction.......................................... 68
2.1.2. TheFischerReaction........................................... 70
2.1.3. TheKoenigs-KnorrReaction................................. 73
2.1.4. TheHelferichReaction........................................ 76
2.1.5. TheFusionReaction............................................ 78
2.1.6. TheImidateReaction........................................... 80
2.1.7. TheSulfurReaction............................................ 88
2.1.8. TheArmed-DisarmedMethod................................ 95
2.1.9. TheGlycalReaction............................................ 98
2.1.10. MiscellaneousLeavingGroups............................... 104
2.1.10.1 FluorideGlycosylDonors......................... 104
2.1.10.2 SilylGlycosylDonors.............................. 105
2.1.10.3 HeterogenousCatalysis............................ 110
2.1.10.4 ThePoolStrategy.................................... 112
2.1.10.5 PhosphateGlycosylDonors....................... 112
2.1.11. EnzymaticApproach........................................... 113
2.1.11.1 EnzymaticSynthesisofOligosaccharides...... 117
2.1.12. TheSolid-PhaseMethodology................................ 117
2.2. CyclicOligosaccharides................................................... 124
2.2.1. ChemoenzymaticandEnzymaticSynthesis................ 127
References........................................................................... 134
3. N-Glycosides........................................................................ 138
3.1. NucleosideFormation...................................................... 139
3.2. ProtectingGroups........................................................... 140
3.2.1. RibofuranosideProtectingGroups........................... 142
3.3. GeneralMethods............................................................ 151
3.3.1. TheMichaelReaction.......................................... 153
3.3.1.1 GeneralFigureandConditions................... 153
3.3.2. TheFischer-HelferichReaction.............................. 156
3.3.2.1 GeneralFigureandConditions................... 156
3.3.3. TheDavol-LowyReaction..................................... 157
3.3.3.1 GeneralFigureandConditions................... 157
3.3.4. SilylCouplingReaction........................................ 159
3.3.4.1 GeneralFigureandConditions................... 159
3.3.5. Sulfur-mediatedReaction...................................... 163
3.3.5.1 GeneralFigureandConditions................... 163
3.3.6. MitsunobuReaction............................................ 163
3.3.7. Palladium-mediatedReaction................................. 164
Contents ix
3.3.8. Microbial/EnzymaticApproach.............................. 166
3.4. OligonucleotideSynthesis................................................. 167
3.4.1. PhosphoramiditeMethod...................................... 170
3.4.2. PhosphonateMethod........................................... 172
3.4.3. ModifiedOligonucleotides.................................... 172
References........................................................................... 176
4. NucleosideMimetics.............................................................. 179
4.1. ModifiedNucleosides...................................................... 180
4.1.1. HeterocycleModifications..................................... 181
4.1.1.1 C-5SubstitutedPyrimidines....................... 181
4.1.1.2 C-6SubstitutedPyrimidines....................... 183
4.1.1.3 PurineFormation.................................... 184
4.1.2. SugarModifications............................................ 185
4.1.2.1 2(cid:2)3(cid:2)-Dideoxysugars.................................. 185
4.1.2.2 2(cid:2)Deoxynucleosides................................. 190
4.1.2.3 3(cid:2)-Deoxynucleosides................................ 192
4.1.2.4 4(cid:2)-SubstitutedNucleosides......................... 193
4.1.3. ComplexNucleosides.......................................... 195
4.1.3.1 FusedHeterocyclicNucleosides.................. 199
4.2. C-Nucleosides............................................................... 200
4.3. CarbocyclicNucleosides.................................................. 209
4.3.1. CyclopropaneCarbocyclicNucleosides.................... 211
4.3.2. CyclobutaneCarbocyclicNucleosides...................... 212
4.3.3. CyclopentaneCarbocyclicNucleosides..................... 212
4.3.4. PalladiumMediated............................................. 214
4.3.5. EnzymaticSynthesis............................................ 220
4.3.5.1 BaseRingFormation............................... 220
4.3.6. CarbocyclicC-Nucleosides.................................... 223
4.4. AcyclicNucleosides........................................................ 223
4.5. Thionucleosides............................................................. 228
4.5.1. PreparationofThioribofuranosylIntermediates........... 230
4.5.2. GlycosidicBondFormation................................... 236
4.5.3. ChloromercurationPromotedCouplingReactions........ 237
4.5.3.1 SilylmediatedCouplingReactions............... 237
References........................................................................... 241
5. C-Glycosides........................................................................ 247
5.1. SyntheticApproachesforthePreparationofC-Glycosides......... 247
5.1.1. ElectrophilicGlycosylDonors................................ 250
5.1.1.1 GlycosylDonorsBearingGood
LeavingGroups...................................... 250
5.1.1.2 OtherElectrophilicGlycosylDonors............ 251
5.1.2. ConcertedReactionandRingFormation................... 255
5.1.3. Palladium-MediatedReactions............................... 256
x Contents
5.1.4. MitsunobuReaction............................................ 256
5.1.5. NucleophilicSugars............................................ 257
5.1.6. Cross-MetathesisReaction.................................... 260
5.1.7. SamariumPromotedReaction................................ 260
5.1.8. TheRamberg-Ba¨cklundReaction............................ 262
5.1.9. FreeRadicalApproach......................................... 263
5.1.10. Exoglycals........................................................ 265
5.1.11. TheTetherApproach........................................... 267
References.......................................................................... 270
6. Glycoconjugates.................................................................. 272
6.1. BiologicalFunctionandStructuralInformation..................... 272
6.1.1. ClassificationofGlycocoproteins............................ 273
6.1.2. RecognitionSites................................................ 275
6.1.3. StructuralInformationofGlycoproteins.................... 276
6.2. CarbohydrateBindingProteins......................................... 277
6.2.1. CombiningSites................................................. 279
6.3. GlycopeptideSynthesis.................................................. 281
6.4. GlycoproteinSynthesis................................................... 285
6.4.1. IndiscriminateGlycosylation................................. 286
6.4.2. ChemoselectiveandSite-SpecificGlycosylation.......... 289
6.4.3. Site-SelectiveGlycosylation.................................. 289
6.4.4. EnzymaticSynthesis............................................ 289
6.5. SynthesisofAntigenicGlycoconjugates.............................. 292
References.......................................................................... 301
7. HydrolysisofGlycosides....................................................... 304
7.1. AcidicHydrolysis......................................................... 304
7.2. BasicHydrolysis........................................................... 306
7.2.1. PhenolicGlycosides............................................ 306
7.2.2. EnolicGlycosides............................................... 306
7.2.3. β-SusbstitutedAlcoholGlycosides.......................... 306
7.3. EnzymaticHydrolysis.................................................... 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. GlycosidaseEnzymaticActivityDetection................. 309
7.3.6. Regardingβ-1,4-Glucanases(EG)........................... 309
7.3.7. Fluorescent O-Glycosides..................................... 310
7.3.8. O-GlycosidesMeasuredbyAbsorption.................... 311
7.3.9. Histochemical O-Glycosides................................. 311
References.......................................................................... 313
8. NuclearMagneticResonanceofGlycosides.............................. 314
8.1. NMRof O-Glycosides................................................... 314
Contents xi
8.2. N-Glycosides............................................................... 325
References.......................................................................... 328
9. X-RayDiffractionofGlycosides............................................. 330
9.1. X-RayDiffractionofO-Glycosides.................................... 331
9.2. X-RayDiffractionofNucleosides...................................... 337
References.......................................................................... 340
10. MassSpectrometryofGlycosides........................................... 342
References.......................................................................... 348
Index...................................................................................... 349