Glycochemical synthesis : strategies and applications

562 Pages·2017·14.783 MB·English

by  Hung, Shang-Cheng, Zulueta, Medel Manuel L

Glycochemical SyntheSiS
Glycochemical
SyntheSiS
Strategies and applications
Edited by
ShanG‐chenG hunG
medel manuel l. Zulueta
Copyright © 2016 by John Wiley & Sons, Inc. All rights reserved
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Library of Congress Cataloguing‐in‐Publication Data:
Names: Hung, Shang-Cheng, editor. | Zulueta, Medel Manuel L., editor.
Title: Glycochemical synthesis : strategies and applications / edited by Shang-Cheng Hung,
Medel Manuel L. Zulueta.
Description: Hoboken, New Jersey : John Wiley & Sons, Inc., [2016] |
Includes bibliographical references and index.
Identifiers: LCCN 2016023028 | ISBN 9781118299845 (cloth)
Subjects: | MESH: Glycoconjugates–chemical synthesis | Glycosylation | Glycomics | Drug Discovery
Classification: LCC QP702.G577 | NLM QU 75 | DDC 572/.567–dc23
LC record available at https://lccn.loc.gov/2016023028
Set in 10/12pt Times by SPi Global, Pondicherry, India
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
CONTENTS
Contributors xv
Foreword xix
Preface xxiii
1 Glycochemistry: Overview and Progress 1
Matthew Schombs and Jacquelyn Gervay‐Hague
1.1 Introduction, 1
1.2 Nomenclature, Structures, and Properties of Sugars, 2
1.2.1 Fischer Projection, 3
1.2.2 Linear Forms of Monosaccharides, 4
1.2.3 Cyclic Forms of Monosaccharides, 6
1.2.4 Haworth and Mills Projections, 6
1.2.5 Reeves Projection, 7
1.2.6 Conformational Analysis, 7
1.2.7 Disaccharides, Oligosaccharides, and Polysaccharides, 10
1.2.8 Anomeric Effect, 11
1.2.9 Mutarotation, 12
1.3 Historical Overview of Carbohydrate Research, 12
1.3.1 Emil Fischer (1852–1919): The Father of Carbohydrate
Chemistry, 13
1.3.2 Koenigs–Knorr Reaction, 15
1.3.3 Karl Freudenberg (1886–1983), 16
1.3.4 Burckhardt Helferich (1887–1982), 16
1.3.5 Hermann Fischer (1888–1960), 17
vi CONTENTS
1.3.6 Claude Hudson (1881–1952), 17
1.3.7 Horace Isbell (1898–1992), 18
1.3.8 Melville Wolfrom (1900–1969), 18
1.3.9 “Sugar” Raymond Lemieux (1920–2000), 19
1.3.10 Ascent of De Novo Sugar Synthesis, 20
1.4 Onward to the Twenty‐First Century, 22
1.4.1 Glycosyl Donors and Glycosylation Systems, 22
1.4.2 Automated and One‐Pot Methods for Oligosaccharide Synthesis, 24
1.4.3 Solid‐Phase Oligosaccharide Synthesis, 25
1.4.4 Natural Product Synthesis, 25
1.4.5 Carbohydrate‐Based Therapeutics, 26
1.5 Conclusion and Outlook, 28
References, 29
2 Protecting Group Strategies in Carbohydrate Synthesis 35
Shang‐Cheng Hung and Cheng‐Chung Wang
2.1 Introduction, 35
2.2 General Considerations for Protecting Group Selection, 36
2.2.1 Retrosynthesis, 36
2.2.2 Neighboring Group Participation, 37
2.2.3 Inductive Effect, 38
2.3 Common Protecting Groups in Carbohydrate Synthesis, 38
2.3.1 Benzyl Ethers, 38
2.3.2 Allyl Ethers, 40
2.3.3 Silyl Ethers, 41
2.3.4 Esters, 42
2.3.5 Amine Protecting Groups, 43
2.3.6 Diol Protection with Acetals and Ketals, 45
2.4 Regioselective Protection of Monosaccharides, 46
2.4.1 Through Differentiation of Primary Hydroxyls Using Bulky
Protecting Groups, 47
2.4.2 Through Protection of Diols with Acetals or Ketals, 50
2.5 One‐Pot Protection Methods, 57
2.6 Conclusion, 61
References, 62
3 General Aspects in O‐Glycosidic Bond Formation 69
Xin‐Shan Ye and Weigang Lu
3.1 Introduction, 69
3.2 Some Basic Concepts, 69
3.2.1 Mechanism of Glycosylation, 70
3.2.2 Stereoselectivity, 70
3.2.3 Anomeric Effect, 70
3.2.4 Participation by Functional Groups in the Glycosyl Donor, 71
3.2.5 The Armed–Disarmed Concept, 72
3.2.6 Additives, 72
CONTENTS vii
3.2.7 Solvent Effect, 73
3.2.8 Effects of Other Factors on Glycosylation, 73
3.3 Methods for Glycosidic Bond Formation, 74
3.3.1 Glycosyl Halides, 74
3.3.2 Glycosyl Trichloroacetimidates, 76
3.3.3 Thioglycosides, 78
3.3.4 n‐Pentenyl Glycosides, 80
3.3.5 Carboxybenzyl Glycosides, 81
3.3.6 Glycosyl Phosphates/Phosphites, 83
3.3.7 Dehydrative Glycosylation, 84
3.3.8 Glycals, 84
3.3.9 Other Glycosylation Protocols, 86
3.4 Glycosylation Strategies, 86
3.4.1 One‐Pot Glycosylation, 87
3.4.2 Solid‐Phase Oligosaccharide Synthesis, 88
3.4.3 Chemoenzymatic Glycosylation, 90
3.5 Conclusion, 91
References, 91
4 Controlling Anomeric Selectivity, Reactivity, and Regioselectivity
in Glycosylations Using Protecting Groups 97
Thomas Jan Boltje, Lin Liu, and Geert‐Jan Boons
4.1 Introduction, 97
4.2 Protecting Group and Control of Anomeric Selectivity
of Glycosylations, 98
4.2.1 Neighboring Group Participation of C2 Esters to Afford
1,2‐trans‐Glycosides, 98
4.2.2 Remote Neighboring Group Participation, 99
4.2.3 Neighboring Group Participation by Other Functional Groups, 100
4.2.4 Neighboring Group Participation Using Chiral Auxiliaries
to Obtain 1,2‐cis‐Glycosides, 103
4.2.5 Intramolecular Aglycone Delivery, 106
4.2.6 Anomeric Control by Electronic and Steric Effects, 108
4.2.7 Conformational Selection Using a 3,5‐O‐Di‐tert‐Butylsilylidene
Protecting Group, 112
4.2.8 Stereoselective Introduction of 2‐Deoxy‐2‐Aminoglycosides, 114
4.3 Use of Protecting Groups for Chemoselective Glycosylations, 115
4.4 Protecting Groups in Regioselective Glycosylations, 118
4.5 Conclusion, 125
References, 125
5 Stereocontrolled Synthesis of Sialosides 131
Chandrasekhar Navuluri and David Crich
5.1 Introduction, 131
5.2 Conformational Analysis of Sialyl Oxocarbenium Ions, 132
5.3 Additives in Sialylations, 133
viii CONTENTS
5.4 Leaving Groups in Sialylations, 134
5.5 Influence of the N5 Protecting Group on Reactivity and Selectivity, 134
5.6 4‐O,5‐N‐Oxazolidinone Group and its Stereodirecting Influence
on Sialylations, 139
5.7 4,5‐O‐Carbonate Protecting Group in α‐Selective KDN Donors, 144
5.8 Other Cyclic and Bicyclic Protecting Systems for Sialyl Donors, 145
5.9 Mechanistic Aspects of Sialylation with Cyclically Protected Sialyl
Donors, 146
5.10 Influence of Hydroxy Protecting Groups on Sialyl Donor Reactivity
and Selectivity, 147
5.11 Stereoselective C‐Sialoside Formation, 148
5.12 Stereoselective S‐Sialoside Formation, 149
5.13 Conclusion, 151
References, 151
6 Strategies for One‐Pot Synthesis of Oligosaccharides 155
Bo Yang, Keisuke Yoshida, and Xuefei Huang
6.1 Introduction, 155
6.2 One‐Pot Glycosylation from the Nonreducing End to the
Reducing End, 156
6.2.1 Reactivity‐Based One‐Pot Glycosylation: Fine‐Tuning
of Anomeric Reactivities, 156
6.2.2 One‐Pot Glycosylation Based on Chemoselective Activation
of Different Types of Glycosyl Donors, 165
6.2.3 Preactivation‐Based Reactivity‐Independent One‐Pot
Glycosylation, 170
6.3 Regioselective One‐Pot Glycosylation: Construction of
Oligosaccharides from the Reducing End to the Nonreducing End, 175
6.4 Hybrid One‐Pot Glycosylation, 179
6.5 Conclusion, 183
Acknowledgments, 183
References, 183
7 Automated Oligosaccharide Synthesis: Techniques and Applications 189
Mattan Hurevich, Jeyakumar Kandasamy, and Peter H. Seeberger
7.1 Introduction, 189
7.2 Challenges and Limitations in Solution‐Phase Oligosaccharide
Synthesis, 190
7.3 Solid‐Phase Oligosaccharide Synthesis, 191
7.3.1 Strategies for Solid‐Phase Oligosaccharide Synthesis, 192
7.4 Automated Oligosaccharide Synthesis, 193
7.4.1 Technological Aspects of Automated Solid‐Phase
Oligosaccharide Synthesis, 193
7.4.2 The First Decade of Automated Synthesis
of Oligosaccharides, 194
CONTENTS ix
7.4.3 Recent Improvements in Automated Oligosaccharide Synthesis, 197
7.4.4 Automated Synthesis of Conjugation‐Ready Oligosaccharides, 197
7.4.5 HPLC‐Assisted Automated Oligosaccharide Synthesis, 199
7.5 Microfluidic Techniques for Oligosaccharide Synthesis, 199
7.6 Conclusion and Outlook, 202
Acknowledgments, 202
References, 202
8 Sugar Synthesis by Microfluidic Techniques 205
Koichi Fukase, Katsunori Tanaka, Yukari Fujimoto, Atsushi Shimoyama, and
Yoshiyuki Manabe
8.1 Introduction, 205
8.2 Microfluidic Glycosylation, 206
8.2.1 Microfluidic α‐Sialylation, 206
8.2.2 Glycosylation with KDO, 212
8.2.3 Stereoselective β‐Mannosylation under the Integrated Microfluidic
and Batch Conditions, 214
8.2.4 Chemical N‐Glycosylation of Asparagine under the Integrated
Microfluidic and Batch Conditions, 215
8.3 Conclusion, 216
References, 217
9 Chemoenzymatic Synthesis of Carbohydrates 221
Kasemsiri Chandarajoti and Jian Liu
9.1 Introduction, 221
9.2 Oligosaccharides and Polysaccharides Produced by GTases, 222
9.3 Chemoenzymatic Synthesis of HS, 223
9.3.1 Biosynthetic Pathway of HS and HS Biosynthetic Enzymes, 224
9.3.2 Application of Biosynthetic Enzymes in HS and Heparin
Oligosaccharide Synthesis, 224
9.3.3 Strategy for Controlled Chemoenzymatic Synthesis, 228
9.4 Conclusion, 231
References, 231
10 Synthesis of Glycosaminoglycans 235
Medel Manuel L. Zulueta, Shu‐Yi Lin, Yu‐Peng Hu, and Shang‐Cheng Hung
10.1 Introduction, 235
10.2 General Strategies, 238
10.3 Synthesis of Derivatives of l‐Idose and IdoA, 240
10.4 Synthesis via Stepwise Solution‐Phase Assembly and Compound
Diversification, 242
10.5 Synthesis via Solution‐Phase One‐Pot Assembly, 250
10.6 Polymer‐Supported Synthesis and Automation, 253
10.7 GAG Mimetics, 256
x CONTENTS
10.8 Conclusion, 257
References, 258
11 Chemical Glycoprotein Synthesis 263
Yasuhiro Kajihara, Masumi Murakami, and Carlo Unverzagt
11.1 Introduction, 263
11.2 Oligosaccharide Structures, 264
11.3 Biosynthesis of Glycoproteins, 265
11.4 Chemical Protein Synthesis, 267
11.4.1 Native Chemical Ligation, 267
11.4.2 NCL without the aa‐Cys Junction, 268
11.5 Synthesis of Glycopeptides, 269
11.6 Synthesis of Glycopeptide‐αthioesters, 270
11.6.1 Safety‐Catch Linker, 271
11.6.2 T hioesterification via Activation of C‐Terminal Carboxylic
Acids, 271
11.6.3 C onvergent Methods for the Synthesis of 
Glycopeptide‐αThioesters, 272
11.6.4 Thioesterification via O→S Transesterification for the Synthesis
of Glycopeptide‐αThioesters, 273
11.6.5 Boc‐SPPS for the Synthesis of
Sialylglycopeptide‐αThioesters, 274
11.7 Chemical Synthesis of Glycoproteins, 275
11.7.1 Antibacterial Glycoprotein Diptericin Bearing Two O‐Linked
GalNAc Residues, 275
11.7.2 Lymphotactin, 276
11.7.3 Bacterial Immunity Protein Im7, 276
11.7.4 MUC‐2, 278
11.7.5 GlyCAM‐1, 279
11.7.6 Monocyte Chemotactic Protein‐3, 280
11.7.7 Ribonuclease, 281
11.7.8 Antifreeze Glycoproteins, 281
11.7.9 Interleukin‐8, 282
11.7.10 Interferon‐β‐1a, 283
11.7.11 Saposin C, 284
11.7.12 Erythropoietin, 285
11.8 Conclusion, 288
References, 288
12 Synthesis of Glycosphingolipids 293
Suvarn S. Kulkarni
12.1 Introduction, 293
12.2 Classification and Nomenclature of GSLs, 294
12.3 Biological Significance of GSLs, 296
CONTENTS xi
12.4 Synthesis of GSLs, 297
12.4.1 Synthesis of Globo‐ and Isoglobo‐Series GSLs, 297
12.4.2 Synthesis of Gangliosides, 310
12.5 Conclusion, 320
References, 320
13 Synthesis of Glycosylphosphatidylinositol Anchors 327
Charles Johnson and Zhongwu Guo
13.1 Introduction, 327
13.2 Synthesis of the Tryp. brucei GPI Anchor, 328
13.3 Synthesis of the Yeast GPI Anchor, 333
13.4 Synthesis of the Rat Brain Thy‐1 GPI Anchor, 335
13.5 Synthesis of Plasmodium falciparum GPI Anchor, 340
13.6 Synthesis of Trypanosoma cruzi GPI Anchor, 344
13.7 Synthesis of a Human Sperm CD52 Antigen GPI Anchor, 349
13.8 Synthesis of a Human Lymphocyte CD52 Antigen GPI Anchor, 351
13.9 Synthesis of the Branched GPI Anchor of Toxoplasma gondii, 354
13.10 Conclusion, 355
Acknowledgment, 356
References, 357
14 Synthesis of Bacterial Cell Envelope Components 361
Akihiro Ishiwata and Yukishige Ito
14.1 Introduction, 361
14.2 Peptidoglycan and Related Glycoconjugates, 362
14.2.1 Lipid I, II, and IV Analogues, 362
14.2.2 Peptidoglycan Fragments, 366
14.3 LPS and Related Glycoconjugates, 371
14.3.1 Lipid A, 371
14.3.2 Oligo‐KDO and Inner‐Core Oligosaccharide, 373
14.3.3 Outer‐Core Polysaccharides, 376
14.3.4 Capsular Polysaccharide, 377
14.3.5 Secondary Cell‐Wall Polysaccharide, 378
14.3.6 Zwitterionic Polysaccharide, 378
14.4 Lipoteichoic Acid, 380
14.5 Mycolyl Arabinogalactan, LAM, and Related Glycoconjugates, 382
14.5.1 Arabinan, Galactan, and Related Glycoconjugates, 382
14.5.2 Mycolates and Related Glycoconjugates, 387
14.5.3 LAM and Related Glycoconjugates, 388
14.6 O ligosaccharides of Bacterial Glycoprotein and Related
Glycoconjugates, 390
14.6.1 O‐Linked Oligosaccharide from Bacillus Collagen‐Like
Protein of Anthracis, 390
14.6.2 N‐Linked Glycans from the Gram‐Negative Bacterium
C. jejuni, 392