Handbook of chemical glycosylation: advances in stereoselectivity and therapeutic relevance
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2008
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| Online Access: | http://d-nb.info/985483504/04 http://deposit.dnb.de/cgi-bin/dokserv?id=2998674&prov=M&dok_var=1&dok_ext=htm Inhaltsverzeichnis |
| Item Description: | Literaturangaben |
| Physical Description: | XXI, 501 S. graph. Darst. 25 cm |
| ISBN: | 9783527317806 |
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| 245 | 1 | 0 | |a Handbook of chemical glycosylation |b advances in stereoselectivity and therapeutic relevance |c ed. by Alexei V. Demchenko |
| 264 | 1 | |a Weinheim |b Wiley-VCH |c 2008 | |
| 300 | |a XXI, 501 S. |b graph. Darst. |c 25 cm | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 500 | |a Literaturangaben | ||
| 650 | 4 | |a Glycosylation | |
| 650 | 4 | |a Immunotherapy |x trends | |
| 650 | 4 | |a Models, Molecular | |
| 650 | 4 | |a Oligomers | |
| 650 | 4 | |a Stereoisomerism | |
| 650 | 0 | 7 | |a Stereoselektivität |0 (DE-588)4247497-8 |2 gnd |9 rswk-swf |
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| 689 | 0 | |5 DE-604 | |
| 700 | 1 | |a Demchenko, Alexei V. |d 1965- |e Sonstige |0 (DE-588)134042557 |4 oth | |
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V
Contents
Preface XV
List of Contributors XIX
1 General Aspects of the Clycosidic Bond Formation 1
Alexei V. Demchenko
1.1 Introduction 1
1.2 Major Types of O-Glycosidic Linkages 1
1.3 Historical Development: Classes of Glycosyl Donors 2
1.4 General Reaction Mechanism 4
1.5 Anomeric Effects 7
1.6 Stereoselectivity of Glycosylation 8
1.6.1 Structure of the Glycosyl Donor 8
1.6.1.1 Protecting Groups 8
1.6.1.2 Leaving Group 9
1.6.2 Structure of the Glycosyl Acceptor 9
1.6.2.1 Position of the Hydroxyl 9
1.6.2.2 Protecting Groups 10
1.6.3 Reaction Conditions 10
1.6.3.1 Solvent Effect 10
1.6.3.2 Promoter (Catalyst), Additions 11
1.6.3.3 Temperature and Pressure 11
1.6.4 Other Factors 11
1.7 Special Cases of Glycosylation 12
1.7.1 Aminosugars 12
1.7.2 Sialosides 13
1.7.3 Synthesis of 2-Deoxyglycosides 15
1.7.4 Synthesis of P-Mannosides 15
1.7.5 Synthesis of Furanosides 16
1.8 Glycosylation and Oligosaccharide Sequencing 16
1.8.1 Leaving-Group-Based Strategies 17
1.8.2 Two-Step Activation and Preactivation Strategies 18
Handbook of Chemical Glycosylation: Advances in Stereoselectivity and Therapeutic Relevance.
Edited by Alexei V. Demchenko.
Copyright © 2008 WILEY-VCH Verlag GmbH Co.KGaA. All rights reserved.
ISBN: 978-3-527-31780-6
VI Contents
1.8.3 Protecting-Group-Based Strategies 19
1.9 Conclusions and Outlook 21
References 21
2 Clycoside Synthesis from Anomeric Halides 29
2.1 Glycosyl Fluorides 29
Shin-ichiro Shoda
2.1.1 Background 29
2.1.2 Synthesis of Glycosyl Fluoride Donors 31
2.1.2.1 Fluorinating Reagents 31
2.1.2.2 Glycosyl Fluorides from Hemiacetals 32
2.1.2.3 Glycosyl Fluorides from Glycosyl Esters 33
2.1.2.4 Glycosyl from Glycosyl Halides 34
2.1.2.5 Glycosyl Fluorides from S-Glycosides 35
2.1.2.6 Glycosyl Fluorides from Other Anomeric Moieties 35
2.1.3 Glycosylation Using Glycosyl Fluorides as Glycosyl Donors 36
2.1.3.1 A Weak Lewis Acid Cleaves the C-F Bond. How Was the
Glycosyl Fluoride Method Discovered? 36
2.1.3.2 Various Promoters Employed in Glycosylation by the Glycosyl
Fluoride Method 38
2.1.3.3 Glycosylations Promoted by Various Promoters 38
2.1.3.4 Glycosylation of Silylated Compounds as Glycosyl Acceptors 41
2.1.3.5 Two-Stage Activation Procedure 42
2.1.3.6 Protecting-Group-Based Strategy 44
2.1.4 Application to Natural Product Synthesis 44
2.1.5 Special Topics 51
2.1.5.1 C-Glycoside Synthesis via O-Glycosylation 51
2.1.5.2 Glycosyl Fluorides for the Synthesis of a Combinatorial Library 51
2.1.5.3 Glycosyl Fluorides as Glycosyl Donors for Chemoenzymatic
Synthesis 52
2.1.6 Conclusions and Future Directions 53
2.1.7 Typical Experimental Procedures 53
2.1.7.1 Preparation of the Glycosyl Donors 53
2.1.7.2 Glycosylation Using Glycosyl Fluorides as Glycosyl Donors 54
References 56
2.2 Glycosyl Chlorides, Bromides and Iodides 59
Swam S. Kulkarni, Jacquelyn Getvay-Hague
2.2.1 Background 59
2.2.2 Glycosyl Chlorides 60
2.2.2.1 Preparation of Glycosyl Chlorides 60
2.2.2.2 Reactions of Glycosyl Chlorides 62
2.2.3 Glycosyl Bromides 66
2.2.3.1 Preparation of Glycosyl Bromides 66
2.2.3.2 Reactivity Patterns and Some Useful Reactions
of Glycosyl Bromides 68
Contents VII
2.2.3.3 Stereoselective Glycosylations Employing Glycosyl Bromides
and Applications 69
2.2.4 Glycosyl Iodides 74
2.2.4.1 Preparation of Glycosyl Iodides 75
2.2.4.2 Reactions of Glycosyl Iodides 77
2.2.5 Conclusions 89
2.2.5.1 General Procedure for One-Pot Glycosylation Using
Glycosyl Iodides 90
References 90
3 Clycoside Synthesis from 1-Oxygen Substituted Clycosyl Donors 95
3.1 Hemiacetals and O-Acyl/Carbonyl Derivatives 95
Daniel A. Ryan, David Y. Cm
3.1.1 Introduction 95
3.1.2 Dehydrative Glycosylation via Electrophilic Activation
of Cl-Hemiacetals 95
3.1.3 Acid Activation of Cl-Hemiacetals 96
3.1.4 Hemiacetal Activation with Silicon Electrophiles 100
3.1.5 Hemiacetal Activation with Phosphorus Electrophiles 103
3.1.6 Hemiacetal Activation with Sulfur Electrophiles 107
3.1.7 Hemiacetal Activation with Carbon Electrophiles 111
3.1.8 Other Methods 114
3.1.9 Glycosylation with Anomeric Esters 116
3.1.9.1 Glycosyl Acetate and Glycosyl Benzoate Donors 117
3.1.10 Activation of O-Carbonyl Derivatives 122
3.1.11 Conclusion 128
3.1.12 Representative Experimental Procedures 128
3.1.12.1 Representative Procedure for Preparation of Cl-Hemiacetal Donors
Through a Peracylation-Selective Anomeric Deacylation
Sequence 128
3.1.12.2 Representative Procedure for Bransted Acid Promoted Glycosylation
with Cl-Hemiacetal Donors Using Methoxyacetic Acid 128
3.1.12.3 Representative Procedure for Lewis Acid Promoted Glycosylation
with Cl-Hemiacetal Donors Using Sn(OTf)2 and
LiC104 129
3.1.12.4 Representative Procedure for Silicon Promoted Glycosylation with
Cl-Hemiacetal Donors Using Me3SiBr and CoBr2 129
3.1.12.5 Representative Procedure for Mitsunobu-Type Glycosylation with
Cl-Hemiacetal Donors and Phenol Glycosyl Acceptors 129
3.1.12.6 Representative Procedure for Appel-Type Glycosylation with
Cl-Hemiacetal Donors 129
3.1.12.7 Representative Procedure for Nosyl Chloride Promoted Glycosylation
with Cl-Hemiacetal Donors 130
3.1.12.8 Representative Procedure for Diphenyl Sulfoxide and Triflic Anhydride
Promoted Glycosylation with Cl-Hemiacetal Donors 130
VIII Contents
3.1.12.9 Representative Procedure for Carbodiimide Promoted Glycosylation
with Cl-Hemiacetal Donors 130
3.1.12.10 Representative Procedure for Carbonyl Promoted Glycosylation with
Cl-Hemiacetal Donors Using Trichloroacetic Anhydride 131
3.1.12.11 Representative Procedure for Lewis Acid Promoted Glycosylation
with Glycosyl Acetate Donors Using SnCl4 131
3.1.12.12 Representative Procedure for Iodotrimethylsilane and Phosphine
Oxide Promoted Glycosylation with Glycosyl Acetate Donors 131
3.1.12.13 Representative Procedure for Lewis Acid Promoted Glycosylation
with TOPCAT Glycosyl Donor Using Silver Triflate 131
3.1.12.14 Representative Procedure for TMS Triflate Promoted Glycosylation
with Glycosyl N-Tosyl Carbamate Donors 132
3.1.12.15 Representative Procedure for Trityl Salt Promoted Glycosylation
with Glycosyl Phenyl Carbonate Donors 132
References 132
3.2 Glycoside Synthesis from 1-Oxygen-Substituted Glycosyl Imidates 143
Xiangming Zhu, Richard R. Schmidt
3.2.1 Introduction 143
3.2.2 Methodological Aspects 144
3.2.2.1 Preparation of Anomeric O-Trichloroacetimidates 144
3.2.2.2 Glycosidation of O-Glycosyl Trichloroacetimidates 145
3.2.3 Synthesis of Oligosaccharides 146
3.2.3.1 P-Glucosides, P-Galactosides, a-Mannosides and Others 146
3.2.3.2 Aminosugar-Containing Oligosaccharides 149
3.2.3.3 1,2-cis Glycosides 155
3.2.3.4 Miscellaneous Oligosaccharides 156
3.2.4 Synthesis of Glycoconjugates 160
3.2.4.1 Glycosphingolipids and Mimics 160
3.2.4.2 Glycosyl Phosphatidyl Inositol Anchors 162
3.2.4.3 Glycosyl Amino Acids and Glycopeptides 163
3.2.4.4 Saponins 166
3.2.4.5 Other Natural Products and Derivatives 168
3.2.4.6 Miscellaneous Glycoconjugates 171
3.2.5 Solid-Phase Oligosaccharide Synthesis 171
3.2.6 Trifluoroacetimidates 174
3.2.6.1 Preparation and Activation 174
3.2.6.2 Application to Target Synthesis 176
3.2.7 Conclusions and Outlook 178
3.2.8 Experimental Procedures 178
3.2.8.1 Typical Procedure for the Preparation of O-Glycosyl
Trichloroacetimidates 178
3.2.8.2 Typical Procedure for the Glycosylation with O-Glycosyl
Trichloroacetimidates 179
3.2.8.3 Typical Procedure for the Preparation of O-Glycosyl N-Phenyl
Trifluoroacetimidates 179
Contents IX
3.2.8.4 Typical Procedure for the Glycosylation with O-Glycosyl N-Phenyl
Trifluoroacetimidates 179
References 179
3.3 Anomeric Transglycosylation 285
Kwan-Soo Kim, Heung-Baejeon
3.3.1 Introduction 185
3.3.2 Alkyl Glycosides 187
3.3.3 Silyl Glycosides 187
3.3.4 Heteroaryl Glycosides 190
3.3.5 2-Hydroxy-3,5-Dinitrobenzoate (DISAL) Glycosides 193
3.3.6 Vinyl Glycosides 194
3.3.7 n-Pentenyl Glycosides 200
3.3.8 2'-Carboxybenzyl Glycosides 212
3.3.9 Conclusions and Outlook 217
3.3.10 Experimental Procedures 218
3.3.10.1 Glycosylation Employing Vinyl Glycosides 218
3.3.10.2 Glycosylation Employing n-Pentenyl Glycosides with NIS/TESOTf 219
3.3.10.3 Glycosylation Employing n-Pentenyl Glycosides with IDCP 219
3.3.10.4 Preparation of n-Pentenyl Glycosides from Glycosyl Bromides 219
3.3.10.5 Glycosylation Employing CB Glycosides with Tf2O 219
3.3.10.6 Preparation of BCB Glycosides from Glycosyl Bromides 220
3.3.10.7 Preparation of CB Glycosides from BCB Glycosides 220
References 220
3.4 Phosphates, Phosphites and Other O-P Derivatives 223
Seiichi Nakamura, Hisanori Nambu, Shunichi Hashimoto
3.4.1 Introduction 223
3.4.2 Glycosyl Phosphates 224
3.4.2.1 Preparation of Glycosyl Phosphates 224
3.4.2.2 Glycosidation Using Glycosyl Phosphates 228
3.4.2.3 Mechanism of Glycosidation Reaction with Glycosyl Phosphates 231
3.4.3 Glycosyl Phosphites 232
3.4.3.1 Preparation of Glycosyl Phosphites 232
3.4.3.2 Glycosidation Using Glycosyl Phosphites 233
3.4.3.3 Mechanism of Glycosidation Reaction with Glycosyl Phosphites 237
3.4.4 Glycosyl Donors Carrying Other Phosphorus-Containing
Leaving Groups 238
3.4.4.1 Glycosyl Dimethylphosphinothioates 238
3.4.4.2 Glycosyl Phosphinimidates and Other N=P Derivatives 238
3.4.4.3 Glycosyl N.N.N1,N'-Tetramethylphosphorodiamidates 239
3.4.4.4 Miscellaneous O-P Derivatives 240
3.4.5 Construction of Other Types of Glycosidic Linkages 241
3.4.5.1 Construction of the P-Mannosidic Linkage 241
3.4.5.2 Construction of 2-Acetamido-2-deoxyglycosidic Linkages 241
3.4.5.3 Construction of 2-Deoxyglycosidic Linkages 243
3.4.5.4 Construction of a-Sialosidic Linkages 244
X I Contents
3.4.6 Chemoselective Glycosidation Strategies 246
3.4.7 Application to the Synthesis of Natural Products 248
3.4.8 Conclusion 249
3.4.9 Experimental Procedures 249
3.4.9.1 Preparation of the Glycosyl Donors 249
3.4.9.2 Glycosidation 252
References 254
4 Clycoside Synthesis from 1 -Sulfur/Selenium-Substituted
Derivatives 261
4.1 Thioglycosides in Oligosaccharide Synthesis 261
Wei Zhong, Geert-Jcm Boons
4.1.1 Preparation and O-Glycosidation of Thioglycosides 261
4.1.2 Preparation of Thioglycosides 261
4.1.3 Indirect Use of Thioglycosides in Glycosidations 263
4.1.4 Direct Use of Thioglycosides in Glycosidations 264
4.1.5 Anomeric Control in Glycosidations of Thioglycosides 267
4.1.6 Glycosylation Strategies Using Thioglycosides 274
4.1.6.1 Chemoselective Glycosylations 274
4.1.6.2 Orthogonal and Semiorthogonal Glycosylations 282
4.1.6.3 Two-Directional Glycosylation Strategies 288
4.1.7 Aglycon Transfer 292
4.1.8 General Procedure for Synthesis of Thioglycosides from Peracetylated
Hexapyranosides Promoted by BF3-Etherate 292
4.1.9 General Procedure for Synthesis of Thioglycosides by Displacement
of Acylated Glycosyl Bromide with Thiolate Anion 293
4.1.10 General Procedure for Synthesis of Sialyl Thioglycosides Using
TMSSMe and TMSOTf 293
4.1.11 General Procedure for Activation of Thioglycosides
with Ph2SO/Tf2O 293
4.1.12 General Procedure for Activation of Thioglycosides
with BSP/TTBP/Tf2O 294
4.1.13 General Procedure for Activation of Sialyl Thioglycosides
with NIS/TfOH 294
References 294
4.2 Sulfoxides, Sulfimides and Sulfones 303
David Crich, Albert A. Bowers
4.2.1 Introduction 303
4.2.2 Donor Preparation 303
4.2.2.1 Sulfoxides 303
4.2.2.2 Sulfimides 306
4.2.2.3 Sulfones 306
4.2.2.4 Other Oxidized Derivatives of Thioglycosides 307
4.2.2.5 1,2-Cyclic Sulfites 307
4.2.3 Glycosylation 307
Contents XI
4.2.3.1 Sulfoxides 307
4.2.3.2 Sulfimides 315
4.2.3.3 Sulfones 316
4.23.4 Cyclic Sulfites 316
4.2.4 Applications in Total Synthesis 317
4.2.5 Special Topics 319
4.2.5.1 Intramolecular Aglycone Delivery (IAD) 319
4.2.5.2 Polymer-Supported Synthesis 321
4.2.5.3 Ring Closing and Glycosylation 321
4.2.5.4 Activation of Thioglycosides by Sulfoxides and
Related Reagents 323
4.2.6 Experimental Procedures 324
4.2.6.1 General Procedure for the Preparation of Glycosyl Sulfoxides 324
4.2.6.2 General Procedure for Sulfoxide Glycosidation 325
4.2.7 Conclusion 325
References 325
4.3 Xanthates, Thioimidates and Other Thio Derivatives 329
Wiesfow Szeja, Crzegorz Crynkiewicz
4.3.1 Introduction 329
4.3.2 Dithiocarbonates - Preparation and Application as
Glycosyl Donors 330
4.3.3 Glycosyl Thioimidates - Preparation and Application as
Glycosyl Donors 335
4.3.4 Glycosyl Thiocyanates as Glycosyl Donors 349
4.3.5 Glycosyl Dithiophosphates as Glycosyl Donors 350
4.3.6 Conclusions 352
4.3.7 Typical Experimental Procedures 353
4.3.7.1 Preparation of Xanthates 353
4.3.7.2 Glycosidation of Xanthates 353
4.3.7.3 Preparation of Thioimidates 356
4.3.7.4 Synthesis of Glycosyl Thiocyanates 356
4.3.7.5 Glycosidation of Thiocyanates 357
4.3.7.6 Synthesis of S-(2-Deoxyglycosyl) Phosphorodithioates 357
4.3.7.7 Glycosidation of Glycosyl Phosphorodithioates 357
References 357
4.4 Selenoglycosides 361
Robert A. Field
4.4.1 Background 361
4.4.2 Selenoglycoside Preparation 362
4.4.3 Selenides as Donors 365
4.4.3.1 Promoters for Selenoglycoside Activation 365
4.4.4 Selenoglycosides as Acceptors 371
4.4.5 Exploiting Selenoglycoside Relative Reactivity
in Oligosaccharide Synthesis 372
4.4.6 Summary 375
XII Contents
4.4.7 Examples of Experimental Procedures 376
4.4.7.1 Typical Procedure for the Preparation of Selenoglycosides
from Glycosyl Bromides 376
4.4.7.2 Typical Procedure for the Preparation of Selenoglycosides
from Glycals 376
4.4.7.3 Typical Procedure for NIS/TfOH-Promoted Glycosylation
with Selenoglycosides 376
4.4.7.4 Typical Procedure for BAHA-Promoted Glycosylation
with Selenoglycosides 377
References 377
5 Other Methods for Clycoside Synthesis 381
5.1 Orthoesters and Related Derivatives 383
Bert Fraser-Reid, J. Cristobal Lopez
5.1.1 Introduction 381
5.1.2 Sugar 1,2-Orthoesters 382
5.1.2.1 1,2-O-Alkyl Orthoesters as Glycosyl Donors - Early Developments 384
5.1.2.2 1,2-O-Cyanoethylidene Derivatives 385
5.1.2.3 1,2-Thioorthoester Derivatives 387
5.1.2.4 Internal Orthoesters 388
5.1.2.5 Miscellaneous Orthoesters 389
5.1.3 Orthoester to Glycoside Rearrangement - The Two-Stage Glycosylation
Method Revisited 390
5.1.3.1 Self-Condensation of Mannose 1,2-Orthoesters: Ready Access
to (1 — 2)-linked Mannose Oligosaccharides 394
5.1.3.2 Rearrangement of Sugar-Sugar Orthoesters Leading to 1,2-cis-Glycosidic
Linkages 394
5.1.4 n-Pentenyl-l,2-Orthoesters: Glycosyl Donors with Novel
Implications 394
5.1.4.1 Divergent-Convergent Synthesis of Glycosylaminoglycan 120 from
Glycosyl Donors and Acceptors Ensuing from NPOEs 396
5.1.4.2 From NPOEs to the 1,2-P-Linked Oligomannans
of Candida albicans 398
5.1.4.3 From NPOEs to the Synthesis of a Malaria Candidate
Glycosylphosphatidylinositol (GPI) 398
5.1.4.4 From NPOEs to the Preparation of Glycolipids for Multivalent
Presentation 399
5.1.4.5 The lipoarabinomannan Components of the Cell Wall Complex
of Mycobacterium tuberculosis: NPOEs in Chemoselective,
Regioselective and Three-Component Double Differential
Glycosidations 401
5.1.4.6 Relevance of NPOEs to the Regioselectivity in the Glycosylation
of Primary Versus Secondary Hydroxyls 405
5.1.4.7 Iterative Regioselective Glycosylations of Unprotected Glycosyl
Donors and Acceptors 407
Contents XIII
5.1.4.8 NPOEs of Furanoses: Key Intermediates in the Elaboration
of the Arabino Fragment of LAM 408
5.1.5 Conclusions and Future Directions 410
5.1.6 Typical Experimental Procedures 411
5.1.6.1 General Procedure for the Preparation of Orthoesters 411
5.1.6.2 General Procedure for Glycosidation with
n-Pentenyl Orthoesters 411
References 412
5.2 Other Methods for Glycoside Synthesis: Dehydro and
Anhydro Derivatives 416
David W. Gammon, Bert F. Sels
5.2.1 Introduction 416
5.2.2 Glycals in Glycoside Synthesis 417
5.2.2.1 Preparation of Glycals 417
5.2.2.2 Glycals as Glycosyl Donors 420
5.2.3 Anhydro Sugars as Glycosyl Donors 436
5.2.3.1 1,2-Anhydro Sugars 436
5.2.3.2 1,6-Anhydro Sugars as Glycosyl Donors 441
5.2.4 Conclusion 443
5.2.5 General Experimental Procedures 444
5.2.5.1 General Method for the Preparation of 2-Deoxy-2-Iodoglycosides
from Glycals 444
5.2.5.2 Preparation of 1,2-Anhydro-tri-O-Benzyl-a-D-Glucose and General
Method for Its Use as a Glycosyl Donor in the Formation
of P-Glycosides 444
5.2.5.3 General Method for the Preparation of 2-Deoxy-2-
Iodoglycosylbenzenesulfonamides from Glycals and Its Use as
Glycosyl Donors in the Synthesis of 2-Benzenesulfonamido-2-
Deoxy-P-Glycosides 444
References 445
5.3 Miscellaneous Glycosyl Donors 449
Kazunobu Toshima
5.3.1 Introduction 449
5.3.2 1-O-Silyl Glycoside 449
5.3.3 Diazirine 450
5.3.4 Telluroglycoside 452
5.3.5 Carbamate 452
5.3.6 2-Iodosulfonamide 453
5.3.7 N-Glycosyl Triazole 453
5.3.8 N-Glycosyl Tetrazole 454
5.3.9 N-Glycosyl Amide 456
5.3.10 DNA and RNA Nucleosides 457
5.3.11 Oxazoline 457
5.3.12 Oxathiine 458
5.3.13 1,6-Lactone 459
XIV Contents
5.3.14 Sulfate 460
5.3.15 1,2-Cyclic Sulfite 461
5.3.16 1,2-Cyclopropane 461
5.3.17 1,2-O-Stannylene Acetal 462
5.3.18 6-Acyl-2H-Pyran-3(6H)-One 463
5.3.19 exo-Methylene 464
5.3.20 Concluding Remarks 465
5.3.21 Typical Experimental Procedure 465
5.3.21.1 General Procedure for the Preparation of Diazirines
from Glycosyl Sulfonates 465
5.3.21.2 General Procedure for the Glycosylation of Diazirines 465
5.3.21.3 General Procedure for the Preparation of Glycosyl Sulfonylcarbamates
from Hemiacetals 465
5.3.21.4 General Procedure for the Glycosylation of Glycosyl
Sulfonylcarbamates 466
5.3.21.5 General Procedure for the Preparation of 1,2-O-Stannyl Acetals
from Hemiacetals and the Glycosylation 466
5.3.21.6 General Procedure for the Preparation of 6-Acyl-2H-Pyran-3(6H)-Ones
froml-(2'-Furyl)-2-tert-Butyldimethylsilanyloxyethan-l-Ols 466
5.3.21.7 General Procedure for the Glycosylation of 6-Acyl-2H-
Pyran-3(6H)-Ones 467
References 467
5.4 The Twenty First Century View of Chemical O-Glycosylation 469
Thomas Ziegler
5.4.1 Indirect and Special Methods 469
5.4.1.1 Intramolecular O-Glycosylation 469
5.4.1.2 Leaving-Group-Based Concept 469
5.4.1.3 Prearranged Glycoside Concept 479
5.4.2 Other Indirect and Special Methods 488
5.4.2.1 [4 +2]CycloadditionsofGlycals 488
5.4.2.2 1,2-Cyclopropanated Sugars 492
References 494
Index 497 |
| adam_txt |
V
Contents
Preface XV
List of Contributors XIX
1 General Aspects of the Clycosidic Bond Formation 1
Alexei V. Demchenko
1.1 Introduction 1
1.2 Major Types of O-Glycosidic Linkages 1
1.3 Historical Development: Classes of Glycosyl Donors 2
1.4 General Reaction Mechanism 4
1.5 Anomeric Effects 7
1.6 Stereoselectivity of Glycosylation 8
1.6.1 Structure of the Glycosyl Donor 8
1.6.1.1 Protecting Groups 8
1.6.1.2 Leaving Group 9
1.6.2 Structure of the Glycosyl Acceptor 9
1.6.2.1 Position of the Hydroxyl 9
1.6.2.2 Protecting Groups 10
1.6.3 Reaction Conditions 10
1.6.3.1 Solvent Effect 10
1.6.3.2 Promoter (Catalyst), Additions 11
1.6.3.3 Temperature and Pressure 11
1.6.4 Other Factors 11
1.7 Special Cases of Glycosylation 12
1.7.1 Aminosugars 12
1.7.2 Sialosides 13
1.7.3 Synthesis of 2-Deoxyglycosides 15
1.7.4 Synthesis of P-Mannosides 15
1.7.5 Synthesis of Furanosides 16
1.8 Glycosylation and Oligosaccharide Sequencing 16
1.8.1 Leaving-Group-Based Strategies 17
1.8.2 Two-Step Activation and Preactivation Strategies 18
Handbook of Chemical Glycosylation: Advances in Stereoselectivity and Therapeutic Relevance.
Edited by Alexei V. Demchenko.
Copyright © 2008 WILEY-VCH Verlag GmbH Co.KGaA. All rights reserved.
ISBN: 978-3-527-31780-6
VI Contents
1.8.3 Protecting-Group-Based Strategies 19
1.9 Conclusions and Outlook 21
References 21
2 Clycoside Synthesis from Anomeric Halides 29
2.1 Glycosyl Fluorides 29
Shin-ichiro Shoda
2.1.1 Background 29
2.1.2 Synthesis of Glycosyl Fluoride Donors 31
2.1.2.1 Fluorinating Reagents 31
2.1.2.2 Glycosyl Fluorides from Hemiacetals 32
2.1.2.3 Glycosyl Fluorides from Glycosyl Esters 33
2.1.2.4 Glycosyl from Glycosyl Halides 34
2.1.2.5 Glycosyl Fluorides from S-Glycosides 35
2.1.2.6 Glycosyl Fluorides from Other Anomeric Moieties 35
2.1.3 Glycosylation Using Glycosyl Fluorides as Glycosyl Donors 36
2.1.3.1 A Weak Lewis Acid Cleaves the C-F Bond. How Was the
Glycosyl Fluoride Method Discovered? 36
2.1.3.2 Various Promoters Employed in Glycosylation by the Glycosyl
Fluoride Method 38
2.1.3.3 Glycosylations Promoted by Various Promoters 38
2.1.3.4 Glycosylation of Silylated Compounds as Glycosyl Acceptors 41
2.1.3.5 Two-Stage Activation Procedure 42
2.1.3.6 Protecting-Group-Based Strategy 44
2.1.4 Application to Natural Product Synthesis 44
2.1.5 Special Topics 51
2.1.5.1 C-Glycoside Synthesis via O-Glycosylation 51
2.1.5.2 Glycosyl Fluorides for the Synthesis of a Combinatorial Library 51
2.1.5.3 Glycosyl Fluorides as Glycosyl Donors for Chemoenzymatic
Synthesis 52
2.1.6 Conclusions and Future Directions 53
2.1.7 Typical Experimental Procedures 53
2.1.7.1 Preparation of the Glycosyl Donors 53
2.1.7.2 Glycosylation Using Glycosyl Fluorides as Glycosyl Donors 54
References 56
2.2 Glycosyl Chlorides, Bromides and Iodides 59
Swam S. Kulkarni, Jacquelyn Getvay-Hague
2.2.1 Background 59
2.2.2 Glycosyl Chlorides 60
2.2.2.1 Preparation of Glycosyl Chlorides 60
2.2.2.2 Reactions of Glycosyl Chlorides 62
2.2.3 Glycosyl Bromides 66
2.2.3.1 Preparation of Glycosyl Bromides 66
2.2.3.2 Reactivity Patterns and Some Useful Reactions
of Glycosyl Bromides 68
Contents VII
2.2.3.3 Stereoselective Glycosylations Employing Glycosyl Bromides
and Applications 69
2.2.4 Glycosyl Iodides 74
2.2.4.1 Preparation of Glycosyl Iodides 75
2.2.4.2 Reactions of Glycosyl Iodides 77
2.2.5 Conclusions 89
2.2.5.1 General Procedure for One-Pot Glycosylation Using
Glycosyl Iodides 90
References 90
3 Clycoside Synthesis from 1-Oxygen Substituted Clycosyl Donors 95
3.1 Hemiacetals and O-Acyl/Carbonyl Derivatives 95
Daniel A. Ryan, David Y. Cm
3.1.1 Introduction 95
3.1.2 Dehydrative Glycosylation via Electrophilic Activation
of Cl-Hemiacetals 95
3.1.3 Acid Activation of Cl-Hemiacetals 96
3.1.4 Hemiacetal Activation with Silicon Electrophiles 100
3.1.5 Hemiacetal Activation with Phosphorus Electrophiles 103
3.1.6 Hemiacetal Activation with Sulfur Electrophiles 107
3.1.7 Hemiacetal Activation with Carbon Electrophiles 111
3.1.8 Other Methods 114
3.1.9 Glycosylation with Anomeric Esters 116
3.1.9.1 Glycosyl Acetate and Glycosyl Benzoate Donors 117
3.1.10 Activation of O-Carbonyl Derivatives 122
3.1.11 Conclusion 128
3.1.12 Representative Experimental Procedures 128
3.1.12.1 Representative Procedure for Preparation of Cl-Hemiacetal Donors
Through a Peracylation-Selective Anomeric Deacylation
Sequence 128
3.1.12.2 Representative Procedure for Bransted Acid Promoted Glycosylation
with Cl-Hemiacetal Donors Using Methoxyacetic Acid 128
3.1.12.3 Representative Procedure for Lewis Acid Promoted Glycosylation
with Cl-Hemiacetal Donors Using Sn(OTf)2 and
LiC104 129
3.1.12.4 Representative Procedure for Silicon Promoted Glycosylation with
Cl-Hemiacetal Donors Using Me3SiBr and CoBr2 129
3.1.12.5 Representative Procedure for Mitsunobu-Type Glycosylation with
Cl-Hemiacetal Donors and Phenol Glycosyl Acceptors 129
3.1.12.6 Representative Procedure for Appel-Type Glycosylation with
Cl-Hemiacetal Donors 129
3.1.12.7 Representative Procedure for Nosyl Chloride Promoted Glycosylation
with Cl-Hemiacetal Donors 130
3.1.12.8 Representative Procedure for Diphenyl Sulfoxide and Triflic Anhydride
Promoted Glycosylation with Cl-Hemiacetal Donors 130
VIII Contents
3.1.12.9 Representative Procedure for Carbodiimide Promoted Glycosylation
with Cl-Hemiacetal Donors 130
3.1.12.10 Representative Procedure for Carbonyl Promoted Glycosylation with
Cl-Hemiacetal Donors Using Trichloroacetic Anhydride 131
3.1.12.11 Representative Procedure for Lewis Acid Promoted Glycosylation
with Glycosyl Acetate Donors Using SnCl4 131
3.1.12.12 Representative Procedure for Iodotrimethylsilane and Phosphine
Oxide Promoted Glycosylation with Glycosyl Acetate Donors 131
3.1.12.13 Representative Procedure for Lewis Acid Promoted Glycosylation
with TOPCAT Glycosyl Donor Using Silver Triflate 131
3.1.12.14 Representative Procedure for TMS Triflate Promoted Glycosylation
with Glycosyl N-Tosyl Carbamate Donors 132
3.1.12.15 Representative Procedure for Trityl Salt Promoted Glycosylation
with Glycosyl Phenyl Carbonate Donors 132
References 132
3.2 Glycoside Synthesis from 1-Oxygen-Substituted Glycosyl Imidates 143
Xiangming Zhu, Richard R. Schmidt
3.2.1 Introduction 143
3.2.2 Methodological Aspects 144
3.2.2.1 Preparation of Anomeric O-Trichloroacetimidates 144
3.2.2.2 Glycosidation of O-Glycosyl Trichloroacetimidates 145
3.2.3 Synthesis of Oligosaccharides 146
3.2.3.1 P-Glucosides, P-Galactosides, a-Mannosides and Others 146
3.2.3.2 Aminosugar-Containing Oligosaccharides 149
3.2.3.3 1,2-cis Glycosides 155
3.2.3.4 Miscellaneous Oligosaccharides 156
3.2.4 Synthesis of Glycoconjugates 160
3.2.4.1 Glycosphingolipids and Mimics 160
3.2.4.2 Glycosyl Phosphatidyl Inositol Anchors 162
3.2.4.3 Glycosyl Amino Acids and Glycopeptides 163
3.2.4.4 Saponins 166
3.2.4.5 Other Natural Products and Derivatives 168
3.2.4.6 Miscellaneous Glycoconjugates 171
3.2.5 Solid-Phase Oligosaccharide Synthesis 171
3.2.6 Trifluoroacetimidates 174
3.2.6.1 Preparation and Activation 174
3.2.6.2 Application to Target Synthesis 176
3.2.7 Conclusions and Outlook 178
3.2.8 Experimental Procedures 178
3.2.8.1 Typical Procedure for the Preparation of O-Glycosyl
Trichloroacetimidates 178
3.2.8.2 Typical Procedure for the Glycosylation with O-Glycosyl
Trichloroacetimidates 179
3.2.8.3 Typical Procedure for the Preparation of O-Glycosyl N-Phenyl
Trifluoroacetimidates 179
Contents IX
3.2.8.4 Typical Procedure for the Glycosylation with O-Glycosyl N-Phenyl
Trifluoroacetimidates 179
References 179
3.3 Anomeric Transglycosylation 285
Kwan-Soo Kim, Heung-Baejeon
3.3.1 Introduction 185
3.3.2 Alkyl Glycosides 187
3.3.3 Silyl Glycosides 187
3.3.4 Heteroaryl Glycosides 190
3.3.5 2-Hydroxy-3,5-Dinitrobenzoate (DISAL) Glycosides 193
3.3.6 Vinyl Glycosides 194
3.3.7 n-Pentenyl Glycosides 200
3.3.8 2'-Carboxybenzyl Glycosides 212
3.3.9 Conclusions and Outlook 217
3.3.10 Experimental Procedures 218
3.3.10.1 Glycosylation Employing Vinyl Glycosides 218
3.3.10.2 Glycosylation Employing n-Pentenyl Glycosides with NIS/TESOTf 219
3.3.10.3 Glycosylation Employing n-Pentenyl Glycosides with IDCP 219
3.3.10.4 Preparation of n-Pentenyl Glycosides from Glycosyl Bromides 219
3.3.10.5 Glycosylation Employing CB Glycosides with Tf2O 219
3.3.10.6 Preparation of BCB Glycosides from Glycosyl Bromides 220
3.3.10.7 Preparation of CB Glycosides from BCB Glycosides 220
References 220
3.4 Phosphates, Phosphites and Other O-P Derivatives 223
Seiichi Nakamura, Hisanori Nambu, Shunichi Hashimoto
3.4.1 Introduction 223
3.4.2 Glycosyl Phosphates 224
3.4.2.1 Preparation of Glycosyl Phosphates 224
3.4.2.2 Glycosidation Using Glycosyl Phosphates 228
3.4.2.3 Mechanism of Glycosidation Reaction with Glycosyl Phosphates 231
3.4.3 Glycosyl Phosphites 232
3.4.3.1 Preparation of Glycosyl Phosphites 232
3.4.3.2 Glycosidation Using Glycosyl Phosphites 233
3.4.3.3 Mechanism of Glycosidation Reaction with Glycosyl Phosphites 237
3.4.4 Glycosyl Donors Carrying Other Phosphorus-Containing
Leaving Groups 238
3.4.4.1 Glycosyl Dimethylphosphinothioates 238
3.4.4.2 Glycosyl Phosphinimidates and Other N=P Derivatives 238
3.4.4.3 Glycosyl N.N.N1,N'-Tetramethylphosphorodiamidates 239
3.4.4.4 Miscellaneous O-P Derivatives 240
3.4.5 Construction of Other Types of Glycosidic Linkages 241
3.4.5.1 Construction of the P-Mannosidic Linkage 241
3.4.5.2 Construction of 2-Acetamido-2-deoxyglycosidic Linkages 241
3.4.5.3 Construction of 2-Deoxyglycosidic Linkages 243
3.4.5.4 Construction of a-Sialosidic Linkages 244
X I Contents
3.4.6 Chemoselective Glycosidation Strategies 246
3.4.7 Application to the Synthesis of Natural Products 248
3.4.8 Conclusion 249
3.4.9 Experimental Procedures 249
3.4.9.1 Preparation of the Glycosyl Donors 249
3.4.9.2 Glycosidation 252
References 254
4 Clycoside Synthesis from 1 -Sulfur/Selenium-Substituted
Derivatives 261
4.1 Thioglycosides in Oligosaccharide Synthesis 261
Wei Zhong, Geert-Jcm Boons
4.1.1 Preparation and O-Glycosidation of Thioglycosides 261
4.1.2 Preparation of Thioglycosides 261
4.1.3 Indirect Use of Thioglycosides in Glycosidations 263
4.1.4 Direct Use of Thioglycosides in Glycosidations 264
4.1.5 Anomeric Control in Glycosidations of Thioglycosides 267
4.1.6 Glycosylation Strategies Using Thioglycosides 274
4.1.6.1 Chemoselective Glycosylations 274
4.1.6.2 Orthogonal and Semiorthogonal Glycosylations 282
4.1.6.3 Two-Directional Glycosylation Strategies 288
4.1.7 Aglycon Transfer 292
4.1.8 General Procedure for Synthesis of Thioglycosides from Peracetylated
Hexapyranosides Promoted by BF3-Etherate 292
4.1.9 General Procedure for Synthesis of Thioglycosides by Displacement
of Acylated Glycosyl Bromide with Thiolate Anion 293
4.1.10 General Procedure for Synthesis of Sialyl Thioglycosides Using
TMSSMe and TMSOTf 293
4.1.11 General Procedure for Activation of Thioglycosides
with Ph2SO/Tf2O 293
4.1.12 General Procedure for Activation of Thioglycosides
with BSP/TTBP/Tf2O 294
4.1.13 General Procedure for Activation of Sialyl Thioglycosides
with NIS/TfOH 294
References 294
4.2 Sulfoxides, Sulfimides and Sulfones 303
David Crich, Albert A. Bowers
4.2.1 Introduction 303
4.2.2 Donor Preparation 303
4.2.2.1 Sulfoxides 303
4.2.2.2 Sulfimides 306
4.2.2.3 Sulfones 306
4.2.2.4 Other Oxidized Derivatives of Thioglycosides 307
4.2.2.5 1,2-Cyclic Sulfites 307
4.2.3 Glycosylation 307
Contents XI
4.2.3.1 Sulfoxides 307
4.2.3.2 Sulfimides 315
4.2.3.3 Sulfones 316
4.23.4 Cyclic Sulfites 316
4.2.4 Applications in Total Synthesis 317
4.2.5 Special Topics 319
4.2.5.1 Intramolecular Aglycone Delivery (IAD) 319
4.2.5.2 Polymer-Supported Synthesis 321
4.2.5.3 Ring Closing and Glycosylation 321
4.2.5.4 Activation of Thioglycosides by Sulfoxides and
Related Reagents 323
4.2.6 Experimental Procedures 324
4.2.6.1 General Procedure for the Preparation of Glycosyl Sulfoxides 324
4.2.6.2 General Procedure for Sulfoxide Glycosidation 325
4.2.7 Conclusion 325
References 325
4.3 Xanthates, Thioimidates and Other Thio Derivatives 329
Wiesfow Szeja, Crzegorz Crynkiewicz
4.3.1 Introduction 329
4.3.2 Dithiocarbonates - Preparation and Application as
Glycosyl Donors 330
4.3.3 Glycosyl Thioimidates - Preparation and Application as
Glycosyl Donors 335
4.3.4 Glycosyl Thiocyanates as Glycosyl Donors 349
4.3.5 Glycosyl Dithiophosphates as Glycosyl Donors 350
4.3.6 Conclusions 352
4.3.7 Typical Experimental Procedures 353
4.3.7.1 Preparation of Xanthates 353
4.3.7.2 Glycosidation of Xanthates 353
4.3.7.3 Preparation of Thioimidates 356
4.3.7.4 Synthesis of Glycosyl Thiocyanates 356
4.3.7.5 Glycosidation of Thiocyanates 357
4.3.7.6 Synthesis of S-(2-Deoxyglycosyl) Phosphorodithioates 357
4.3.7.7 Glycosidation of Glycosyl Phosphorodithioates 357
References 357
4.4 Selenoglycosides 361
Robert A. Field
4.4.1 Background 361
4.4.2 Selenoglycoside Preparation 362
4.4.3 Selenides as Donors 365
4.4.3.1 Promoters for Selenoglycoside Activation 365
4.4.4 Selenoglycosides as Acceptors 371
4.4.5 Exploiting Selenoglycoside Relative Reactivity
in Oligosaccharide Synthesis 372
4.4.6 Summary 375
XII Contents
4.4.7 Examples of Experimental Procedures 376
4.4.7.1 Typical Procedure for the Preparation of Selenoglycosides
from Glycosyl Bromides 376
4.4.7.2 Typical Procedure for the Preparation of Selenoglycosides
from Glycals 376
4.4.7.3 Typical Procedure for NIS/TfOH-Promoted Glycosylation
with Selenoglycosides 376
4.4.7.4 Typical Procedure for BAHA-Promoted Glycosylation
with Selenoglycosides 377
References 377
5 Other Methods for Clycoside Synthesis 381
5.1 Orthoesters and Related Derivatives 383
Bert Fraser-Reid, J. Cristobal Lopez
5.1.1 Introduction 381
5.1.2 Sugar 1,2-Orthoesters 382
5.1.2.1 1,2-O-Alkyl Orthoesters as Glycosyl Donors - Early Developments 384
5.1.2.2 1,2-O-Cyanoethylidene Derivatives 385
5.1.2.3 1,2-Thioorthoester Derivatives 387
5.1.2.4 Internal Orthoesters 388
5.1.2.5 Miscellaneous Orthoesters 389
5.1.3 Orthoester to Glycoside Rearrangement - The Two-Stage Glycosylation
Method Revisited 390
5.1.3.1 Self-Condensation of Mannose 1,2-Orthoesters: Ready Access
to (1 — 2)-linked Mannose Oligosaccharides 394
5.1.3.2 Rearrangement of Sugar-Sugar Orthoesters Leading to 1,2-cis-Glycosidic
Linkages 394
5.1.4 n-Pentenyl-l,2-Orthoesters: Glycosyl Donors with Novel
Implications 394
5.1.4.1 Divergent-Convergent Synthesis of Glycosylaminoglycan 120 from
Glycosyl Donors and Acceptors Ensuing from NPOEs 396
5.1.4.2 From NPOEs to the 1,2-P-Linked Oligomannans
of Candida albicans 398
5.1.4.3 From NPOEs to the Synthesis of a Malaria Candidate
Glycosylphosphatidylinositol (GPI) 398
5.1.4.4 From NPOEs to the Preparation of Glycolipids for Multivalent
Presentation 399
5.1.4.5 The lipoarabinomannan Components of the Cell Wall Complex
of Mycobacterium tuberculosis: NPOEs in Chemoselective,
Regioselective and Three-Component Double Differential
Glycosidations 401
5.1.4.6 Relevance of NPOEs to the Regioselectivity in the Glycosylation
of Primary Versus Secondary Hydroxyls 405
5.1.4.7 Iterative Regioselective Glycosylations of Unprotected Glycosyl
Donors and Acceptors 407
Contents XIII
5.1.4.8 NPOEs of Furanoses: Key Intermediates in the Elaboration
of the Arabino Fragment of LAM 408
5.1.5 Conclusions and Future Directions 410
5.1.6 Typical Experimental Procedures 411
5.1.6.1 General Procedure for the Preparation of Orthoesters 411
5.1.6.2 General Procedure for Glycosidation with
n-Pentenyl Orthoesters 411
References 412
5.2 Other Methods for Glycoside Synthesis: Dehydro and
Anhydro Derivatives 416
David W. Gammon, Bert F. Sels
5.2.1 Introduction 416
5.2.2 Glycals in Glycoside Synthesis 417
5.2.2.1 Preparation of Glycals 417
5.2.2.2 Glycals as Glycosyl Donors 420
5.2.3 Anhydro Sugars as Glycosyl Donors 436
5.2.3.1 1,2-Anhydro Sugars 436
5.2.3.2 1,6-Anhydro Sugars as Glycosyl Donors 441
5.2.4 Conclusion 443
5.2.5 General Experimental Procedures 444
5.2.5.1 General Method for the Preparation of 2-Deoxy-2-Iodoglycosides
from Glycals 444
5.2.5.2 Preparation of 1,2-Anhydro-tri-O-Benzyl-a-D-Glucose and General
Method for Its Use as a Glycosyl Donor in the Formation
of P-Glycosides 444
5.2.5.3 General Method for the Preparation of 2-Deoxy-2-
Iodoglycosylbenzenesulfonamides from Glycals and Its Use as
Glycosyl Donors in the Synthesis of 2-Benzenesulfonamido-2-
Deoxy-P-Glycosides 444
References 445
5.3 Miscellaneous Glycosyl Donors 449
Kazunobu Toshima
5.3.1 Introduction 449
5.3.2 1-O-Silyl Glycoside 449
5.3.3 Diazirine 450
5.3.4 Telluroglycoside 452
5.3.5 Carbamate 452
5.3.6 2-Iodosulfonamide 453
5.3.7 N-Glycosyl Triazole 453
5.3.8 N-Glycosyl Tetrazole 454
5.3.9 N-Glycosyl Amide 456
5.3.10 DNA and RNA Nucleosides 457
5.3.11 Oxazoline 457
5.3.12 Oxathiine 458
5.3.13 1,6-Lactone 459
XIV Contents
5.3.14 Sulfate 460
5.3.15 1,2-Cyclic Sulfite 461
5.3.16 1,2-Cyclopropane 461
5.3.17 1,2-O-Stannylene Acetal 462
5.3.18 6-Acyl-2H-Pyran-3(6H)-One 463
5.3.19 exo-Methylene 464
5.3.20 Concluding Remarks 465
5.3.21 Typical Experimental Procedure 465
5.3.21.1 General Procedure for the Preparation of Diazirines
from Glycosyl Sulfonates 465
5.3.21.2 General Procedure for the Glycosylation of Diazirines 465
5.3.21.3 General Procedure for the Preparation of Glycosyl Sulfonylcarbamates
from Hemiacetals 465
5.3.21.4 General Procedure for the Glycosylation of Glycosyl
Sulfonylcarbamates 466
5.3.21.5 General Procedure for the Preparation of 1,2-O-Stannyl Acetals
from Hemiacetals and the Glycosylation 466
5.3.21.6 General Procedure for the Preparation of 6-Acyl-2H-Pyran-3(6H)-Ones
froml-(2'-Furyl)-2-tert-Butyldimethylsilanyloxyethan-l-Ols 466
5.3.21.7 General Procedure for the Glycosylation of 6-Acyl-2H-
Pyran-3(6H)-Ones 467
References 467
5.4 The Twenty First Century View of Chemical O-Glycosylation 469
Thomas Ziegler
5.4.1 Indirect and Special Methods 469
5.4.1.1 Intramolecular O-Glycosylation 469
5.4.1.2 Leaving-Group-Based Concept 469
5.4.1.3 Prearranged Glycoside Concept 479
5.4.2 Other Indirect and Special Methods 488
5.4.2.1 [4 +2]CycloadditionsofGlycals 488
5.4.2.2 1,2-Cyclopropanated Sugars 492
References 494
Index 497 |
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| id | DE-604.BV023328123 |
| illustrated | Illustrated |
| index_date | 2024-07-02T20:56:30Z |
| indexdate | 2024-07-20T09:41:08Z |
| institution | BVB |
| isbn | 9783527317806 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-016512103 |
| oclc_num | 174131473 |
| open_access_boolean | |
| owner | DE-19 DE-BY-UBM DE-91S DE-BY-TUM DE-29T |
| owner_facet | DE-19 DE-BY-UBM DE-91S DE-BY-TUM DE-29T |
| physical | XXI, 501 S. graph. Darst. 25 cm |
| publishDate | 2008 |
| publishDateSearch | 2008 |
| publishDateSort | 2008 |
| publisher | Wiley-VCH |
| record_format | marc |
| spelling | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance ed. by Alexei V. Demchenko Weinheim Wiley-VCH 2008 XXI, 501 S. graph. Darst. 25 cm txt rdacontent n rdamedia nc rdacarrier Literaturangaben Glycosylation Immunotherapy trends Models, Molecular Oligomers Stereoisomerism Stereoselektivität (DE-588)4247497-8 gnd rswk-swf Glykosylierung (DE-588)4269099-7 gnd rswk-swf Glykosylierung (DE-588)4269099-7 s Stereoselektivität (DE-588)4247497-8 s DE-604 Demchenko, Alexei V. 1965- Sonstige (DE-588)134042557 oth http://d-nb.info/985483504/04 http://deposit.dnb.de/cgi-bin/dokserv?id=2998674&prov=M&dok_var=1&dok_ext=htm HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016512103&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance Glycosylation Immunotherapy trends Models, Molecular Oligomers Stereoisomerism Stereoselektivität (DE-588)4247497-8 gnd Glykosylierung (DE-588)4269099-7 gnd |
| subject_GND | (DE-588)4247497-8 (DE-588)4269099-7 |
| title | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance |
| title_auth | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance |
| title_exact_search | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance |
| title_exact_search_txtP | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance |
| title_full | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance ed. by Alexei V. Demchenko |
| title_fullStr | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance ed. by Alexei V. Demchenko |
| title_full_unstemmed | Handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance ed. by Alexei V. Demchenko |
| title_short | Handbook of chemical glycosylation |
| title_sort | handbook of chemical glycosylation advances in stereoselectivity and therapeutic relevance |
| title_sub | advances in stereoselectivity and therapeutic relevance |
| topic | Glycosylation Immunotherapy trends Models, Molecular Oligomers Stereoisomerism Stereoselektivität (DE-588)4247497-8 gnd Glykosylierung (DE-588)4269099-7 gnd |
| topic_facet | Glycosylation Immunotherapy trends Models, Molecular Oligomers Stereoisomerism Stereoselektivität Glykosylierung |
| url | http://d-nb.info/985483504/04 http://deposit.dnb.de/cgi-bin/dokserv?id=2998674&prov=M&dok_var=1&dok_ext=htm http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=016512103&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT demchenkoalexeiv handbookofchemicalglycosylationadvancesinstereoselectivityandtherapeuticrelevance |