Glycochemical Synthesis Strategies and Applications

Shang-Cheng Hung, PhD, is a Distinguished Research Fellow of the Genomics Research Center, Academia Sinica, Taiwan. His work focuses on carbohydrate chemistry and chemical biology, including the development of novel approaches to glycan synthesis and the acquisition of important cell-surface glycan components together with their biological evaluations.

Medel Manuel L. Zulueta, PhD, is a carbohydrate chemist at the Genomics Research Center, Academia Sinica, Taiwan. He develops of strategies for the chemical synthesis of oligosaccharides, particularly heparin and heparan sulfate.

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

1.3 Historical Overview of Carbohydrate Research, 12

1.4 Onward to the Twenty-First Century, 22

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

2.3 Common Protecting Groups in Carbohydrate Synthesis, 38

2.4 Regioselective Protection of Monosaccharides, 46

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

3.3 Methods for Glycosidic Bond Formation, 74

3.4 Glycosylation Strategies, 86

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

4.3 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

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

6.3 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

7.4 Automated Oligosaccharide Synthesis, 193

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

8.3 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

9.4 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

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

11.5 Synthesis of Glycopeptides, 269

11.6 Synthesis of Glycopeptide-αthioesters, 270

11.7 Chemical Synthesis of Glycoproteins, 275

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

12.4 Synthesis of GSLs, 297

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

14.3 LPS and Related Glycoconjugates, 371

14.4 Lipoteichoic Acid, 380

14.5 Mycolyl Arabinogalactan, LAM, and Related Glycoconjugates, 382

14.6 Oligosaccharides of Bacterial Glycoprotein and Related Glycoconjugates, 390

14.7 Conclusion, 394

References, 395

15 Discoveries and Applications of Glycan Arrays 407
Chung-Yi Wu and Shih-Huang Chang

15.1 Introduction, 407

15.2 Discoveries of Glycan Arrays, 407

15.3 Applications of Glycan Array, 412

15.4 Conclusion, 418

References, 418

16 Synthesis and Applications of Glyconanoparticles, Glycodendrimers, and Glycoclusters in Biological Systems 425
Avijit Kumar Adak, Ching-Ching Yu, and Chun-Cheng Lin

16.1 Introduction, 425

16.2 Significance of Multivalent Binding Interactions in Biological Systems, 426

16.3 Glyconanoparticles, Glycodendrimers, and Glycoclusters: General Overview, 428

16.4 Plant Lectins, 431

16.5 AB5 Toxins, 438

16.6 Bacterial Adhesion Lectins, 440

16.7 Influenza Virus, 445

16.8 Detection of Bacteria, 445

16.9 Glyco-MNPs as Nanoprobes for Labeling Cells and Magnetic Resonance Imaging Agents, 446

16.10 Cyclopeptide-Based Glycoclusters as Vaccine Adjuvants, 447

16.11 Conclusion, 449

Acknowledgments, 449

References, 450

17 Design and Synthesis of Carbohydrates and Carbohydrate Mimetics as Anti-Influenza Agents 455
Mauro Pascolutti and Mark von Itzstein

17.1 Introduction, 455

17.2 Influenza Viruses, 456

17.3 Development of Anti-Influenza Therapeutics, 459

17.4 Sialic Acid: The Viral Cell-Surface Receptor Ligand, 460

17.5 Hemagglutinin, 460

17.6 Sialidase, 461

17.7 Influenza Virus Sialidase as a Drug Discovery Target, 464

17.8 Structural Differences Recently Identified in Influenza a Virus Sialidase Subtypes, 471

17.9 New Influenza Virus Sialidase Inhibitors Targeting the 150-Cavity, 473

References, 476

18 Design and Synthesis of Ligands and Antagonists of Siglecs as Immune Response Modifiers 483
Hajjaj H. M. Abdu-Allah, Hideharu Ishida, and Makoto Kiso

18.1 Introduction, 483

18.2 Lectins, 484

18.3 Siglecs, 484

18.4 Siglecs and Innate Immunity, 489

18.5 Design and Synthesis of High-Affinity Ligands for Siglecs, 494

18.6 Conclusion and Future Directions, 501

References, 502

19 Sugar–Protein Hybrids for Biomedical Applications 509
Macarena Sánchez-Navarro and Benjamin G. Davis

19.1 Introduction, 509

19.2 Challenges in the Development of Glycoprotein-Based Therapeutics, 510

19.3 Why Unnatural? 510

19.4 Retrosynthetic Analysis, 511

19.5 Linkages, 512

19.6 Glycoprotein-Based Therapeutics, 521

19.7 Conclusion, 527

References, 527

Index 535

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