Glycochemical Synthesis

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 xvForeword xixPreface xxiii1 Glycochemistry: Overview and Progress 1Matthew Schombs and Jacquelyn Gervay-Hague1.1 Introduction, 11.2 Nomenclature, Structures, and Properties of Sugars, 21.3 Historical Overview of Carbohydrate Research, 121.4 Onward to the Twenty-First Century, 221.5 Conclusion and Outlook, 28References, 292 Protecting Group Strategies in Carbohydrate Synthesis 35Shang-Cheng Hung and Cheng-Chung Wang2.1 Introduction, 352.2 General Considerations for Protecting Group Selection, 362.3 Common Protecting Groups in Carbohydrate Synthesis, 382.4 Regioselective Protection of Monosaccharides, 462.5 One-Pot Protection Methods, 572.6 Conclusion, 61References, 623 General Aspects in O-Glycosidic Bond Formation 69Xin-Shan Ye and Weigang Lu3.1 Introduction, 693.2 Some Basic Concepts, 693.3 Methods for Glycosidic Bond Formation, 743.4 Glycosylation Strategies, 863.5 Conclusion, 91References, 914 Controlling Anomeric Selectivity, Reactivity, and Regioselectivity in Glycosylations Using Protecting Groups 97Thomas Jan Boltje, Lin Liu, and Geert-Jan Boons4.1 Introduction, 974.2 Protecting Group and Control of Anomeric Selectivity of Glycosylations, 984.3 Use of Protecting Groups for Chemoselective Glycosylations, 1154.4 Protecting Groups in Regioselective Glycosylations, 1184.5 Conclusion, 125References, 1255 Stereocontrolled Synthesis of Sialosides 131Chandrasekhar Navuluri and David Crich5.1 Introduction, 1315.2 Conformational Analysis of Sialyl Oxocarbenium Ions, 1325.3 Additives in Sialylations, 1335.4 Leaving Groups in Sialylations, 1345.5 Influence of the N5 Protecting Group on Reactivity and Selectivity, 1345.6 4-O,5-N-Oxazolidinone Group and its Stereodirecting Influence on Sialylations, 1395.7 4,5-O-Carbonate Protecting Group in α-Selective KDN Donors, 1445.8 Other Cyclic and Bicyclic Protecting Systems for Sialyl Donors, 1455.9 Mechanistic Aspects of Sialylation with Cyclically Protected Sialyl Donors, 1465.10 Influence of Hydroxy Protecting Groups on Sialyl Donor Reactivity and Selectivity, 1475.11 Stereoselective C-Sialoside Formation, 1485.12 Stereoselective S-Sialoside Formation, 1495.13 Conclusion, 151References, 1516 Strategies for One-Pot Synthesis of Oligosaccharides 155Bo Yang, Keisuke Yoshida, and Xuefei Huang6.1 Introduction, 1556.2 One-Pot Glycosylation from the Nonreducing End to the Reducing End, 1566.3 Regioselective One-Pot Glycosylation: Construction of Oligosaccharides from the Reducing End to the Nonreducing End, 1756.4 Hybrid One-Pot Glycosylation, 1796.5 Conclusion, 183Acknowledgments, 183References, 1837 Automated Oligosaccharide Synthesis: Techniques and Applications 189Mattan Hurevich, Jeyakumar Kandasamy, and Peter H. Seeberger7.1 Introduction, 1897.2 Challenges and Limitations in Solution-Phase Oligosaccharide Synthesis, 1907.3 Solid-Phase Oligosaccharide Synthesis, 1917.4 Automated Oligosaccharide Synthesis, 1937.5 Microfluidic Techniques for Oligosaccharide Synthesis, 1997.6 Conclusion and Outlook, 202Acknowledgments, 202References, 2028 Sugar Synthesis by Microfluidic Techniques 205Koichi Fukase, Katsunori Tanaka, Yukari Fujimoto, Atsushi Shimoyama, and Yoshiyuki Manabe8.1 Introduction, 2058.2 Microfluidic Glycosylation, 2068.3 Conclusion, 216References, 2179 Chemoenzymatic Synthesis of Carbohydrates 221Kasemsiri Chandarajoti and Jian Liu9.1 Introduction, 2219.2 Oligosaccharides and Polysaccharides Produced by GTases, 2229.3 Chemoenzymatic Synthesis of HS, 2239.4 Conclusion, 231References, 23110 Synthesis of Glycosaminoglycans 235Medel Manuel L. Zulueta, Shu-Yi Lin, Yu-Peng Hu, and Shang-Cheng Hung10.1 Introduction, 23510.2 General Strategies, 23810.3 Synthesis of Derivatives of l-Idose and IdoA, 24010.4 Synthesis via Stepwise Solution-Phase Assembly and Compound Diversification, 24210.5 Synthesis via Solution-Phase One-Pot Assembly, 25010.6 Polymer-Supported Synthesis and Automation, 25310.7 GAG Mimetics, 25610.8 Conclusion, 257References, 25811 Chemical Glycoprotein Synthesis 263Yasuhiro Kajihara, Masumi Murakami, and Carlo Unverzagt11.1 Introduction, 26311.2 Oligosaccharide Structures, 26411.3 Biosynthesis of Glycoproteins, 26511.4 Chemical Protein Synthesis, 26711.5 Synthesis of Glycopeptides, 26911.6 Synthesis of Glycopeptide-αthioesters, 27011.7 Chemical Synthesis of Glycoproteins, 27511.8 Conclusion, 288References, 28812 Synthesis of Glycosphingolipids 293Suvarn S. Kulkarni12.1 Introduction, 29312.2 Classification and Nomenclature of GSLs, 29412.3 Biological Significance of GSLs, 29612.4 Synthesis of GSLs, 29712.5 Conclusion, 320References, 32013 Synthesis of Glycosylphosphatidylinositol Anchors 327Charles Johnson and Zhongwu Guo13.1 Introduction, 32713.2 Synthesis of the Tryp. brucei GPI Anchor, 32813.3 Synthesis of the Yeast GPI Anchor, 33313.4 Synthesis of the Rat Brain Thy-1 GPI Anchor, 33513.5 Synthesis of Plasmodium falciparum GPI Anchor, 34013.6 Synthesis of Trypanosoma cruzi GPI Anchor, 34413.7 Synthesis of a Human Sperm CD52 Antigen GPI Anchor, 34913.8 Synthesis of a Human Lymphocyte CD52 Antigen GPI Anchor, 35113.9 Synthesis of the Branched GPI Anchor of Toxoplasma gondii, 35413.10 Conclusion, 355Acknowledgment, 356References, 35714 Synthesis of Bacterial Cell Envelope Components 361Akihiro Ishiwata and Yukishige Ito14.1 Introduction, 36114.2 Peptidoglycan and Related Glycoconjugates, 36214.3 LPS and Related Glycoconjugates, 37114.4 Lipoteichoic Acid, 38014.5 Mycolyl Arabinogalactan, LAM, and Related Glycoconjugates, 38214.6 Oligosaccharides of Bacterial Glycoprotein and Related Glycoconjugates, 39014.7 Conclusion, 394References, 39515 Discoveries and Applications of Glycan Arrays 407Chung-Yi Wu and Shih-Huang Chang15.1 Introduction, 40715.2 Discoveries of Glycan Arrays, 40715.3 Applications of Glycan Array, 41215.4 Conclusion, 418References, 41816 Synthesis and Applications of Glyconanoparticles, Glycodendrimers, and Glycoclusters in Biological Systems 425Avijit Kumar Adak, Ching-Ching Yu, and Chun-Cheng Lin16.1 Introduction, 42516.2 Significance of Multivalent Binding Interactions in Biological Systems, 42616.3 Glyconanoparticles, Glycodendrimers, and Glycoclusters: General Overview, 42816.4 Plant Lectins, 43116.5 AB5 Toxins, 43816.6 Bacterial Adhesion Lectins, 44016.7 Influenza Virus, 44516.8 Detection of Bacteria, 44516.9 Glyco-MNPs as Nanoprobes for Labeling Cells and Magnetic Resonance Imaging Agents, 44616.10 Cyclopeptide-Based Glycoclusters as Vaccine Adjuvants, 44716.11 Conclusion, 449Acknowledgments, 449References, 45017 Design and Synthesis of Carbohydrates and Carbohydrate Mimetics as Anti-Influenza Agents 455Mauro Pascolutti and Mark von Itzstein17.1 Introduction, 45517.2 Influenza Viruses, 45617.3 Development of Anti-Influenza Therapeutics, 45917.4 Sialic Acid: The Viral Cell-Surface Receptor Ligand, 46017.5 Hemagglutinin, 46017.6 Sialidase, 46117.7 Influenza Virus Sialidase as a Drug Discovery Target, 46417.8 Structural Differences Recently Identified in Influenza a Virus Sialidase Subtypes, 47117.9 New Influenza Virus Sialidase Inhibitors Targeting the 150-Cavity, 473References, 47618 Design and Synthesis of Ligands and Antagonists of Siglecs as Immune Response Modifiers 483Hajjaj H. M. Abdu-Allah, Hideharu Ishida, and Makoto Kiso18.1 Introduction, 48318.2 Lectins, 48418.3 Siglecs, 48418.4 Siglecs and Innate Immunity, 48918.5 Design and Synthesis of High-Affinity Ligands for Siglecs, 49418.6 Conclusion and Future Directions, 501References, 50219 Sugar–Protein Hybrids for Biomedical Applications 509Macarena Sánchez-Navarro and Benjamin G. Davis19.1 Introduction, 50919.2 Challenges in the Development of Glycoprotein-Based Therapeutics, 51019.3 Why Unnatural? 51019.4 Retrosynthetic Analysis, 51119.5 Linkages, 51219.6 Glycoprotein-Based Therapeutics, 52119.7 Conclusion, 527References, 527Index 535