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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