Table of Contents Volume 1 1 General Principles 1 1.1 Structure and Conformation of Carbohydrates 3 T. Bruce Grindley 1.2 General Properties, Occurrence, and Preparation of Carbohydrates 57 John F. Robyt 2 General Synthetic Methods 101 2.1 Reactions at Oxygen Atoms 103 Ana M. Gomez 2.2 Oxidation, Reduction, and Deoxygenation 179 Robert Madsen 2.3 Heteroatom Exchange 227 Yuhang Wang, Xin-Shan Ye 2.4 Anhydrosugars 271 Slawomir Jarosz, Marcin Nowogmdzki 2.5 C-C Bond Formation 305 Yuguo Du, Qi Chen, Jim Liu 2.6 C=C Bond Formation 343 Slawomir Jarosz, Marcin Nowogrodzki 2.7 Degradations and Rearrangement Reactions 375 Jianbo Zhang Bibliografische Informationen digitalisiert durch http://d-nb.info/980124565 gescannt durch Table of Contents 3 Chemical Glycosylation Reactions 427 3.1 Glycosyl Halides 429 Kazunobu Toshima 3.2 Glycosyl Trichloroacetimidates 451 Richard R. Schmidt, Xiangming Zhu 3.3 Further Anomeric Esters 525 Kwan Soo Kim, Heung Bae Jeon 3.4 O-Glycosyl Donors 565 J. Cristobal Lopez 3.5 S-Glycosylation 661 Stefan Oscarson 3.6 Glycal Derivatives 699 Waldemar Priebe, Izabela Fokt, Grzegorz Grynkiewicz 3.7 Anomeric Anhydro Sugars 737 Nathan W. McGill, Spencer J. Williams 3.8 C-Glycosylation 755 Toshio Nishikawa, Masaatsu Adachi, Minoru Isobe Volume 2 4 Monosaccharides 813 4.1 Monosaccharides: Occurrence, Significance, and Properties . 815 Zbigniew J. Witczak 4.2 Monosaccharides and Polyols in Foods 841 Robert B. Friedman 4.3 De novo Synthesis of Monosaccharides 857 Pierre Vogel, Inmaculada Robina 4.4 Monosaccharides as Chiral Pools for the Synthesis of Complex Natural Compounds 957 Masaya Nakata Table of Contents XI 4.5 Monosaccharides as Scaffolds for the Synthesis of Novel Compounds 995 Paul V. Murphy, Trinidad Velasco-Torrijos 4.6 Monosaccharides as Chiral Auxiliaries and Ligands for Asymmetric Synthesis 1029 Kiichiro Totani, Kin-ichi Tadano 4.7 Carbohydrate-Metal Complexes: Structural Chemistry of Stable Solution Species 1077 Thorsten Allscher, Peter Klufers, Peter Mayer 5 Oligosaccharides 1141 5.1 Oligosaccharides: Occurrence, Significance, and Properties .. 1143 Zbigniew J. Witczak 5.2 Sucrose and Related Oligosaccharides 1163 Gillian Eggleston 5.3 Oligosaccharides in Food and Agriculture 1185 Michelle E. Collins, Robert A. Rastall 5.4 Combinatorial Methods in Oligosaccharide Synthesis 1205 Katsunori Tanaka, Yukari Fujimoto, Shin-ichi Tanaka, Yasutaka Mori, Koichi Fukase 5.5 Polymer-Supported and Tag-Assisted Methods in Oligosaccharide Synthesis 1241 Katsunori Tanaka, Koichi Fukase 5.6 Stereoselective Synthesis of /?-manno-Glycosides 1279 Akihiro Ishiwata, Yukishige Ito 5.7 Selective a-Sialylation 1313 Hiromune Ando, Makoto Kiso 5.8 Enzymatic Glycosylation by Transferases 1361 Ola Blixt, Nahid Razi 5.9 Enzymatic Glycosylation by Glycohydrolases and Glycosynthases 1387 Julian Thimm, Joachim Thiem XII Table of Contents 6 Complex Polysaccharides 1411 6.1 Polysaccharides: Occurrence, Significance, and Properties ... 1413 James N. BeMiller 6.2 Starch: Structure, Properties, Chemistry, and Enzymology .... 1437 John F. Robyt 6.3 Cellulose and Associated Heteropolysaccharides 1473 Wolfgang G. Glasser 6.4 Gums and Related Polysaccharides 1513 James N. BeMiller 6.5 Bacterial Cell Wall Components 1535 Cynthia Ginsberg, Stephanie Brown, Suzanne Walker 7 Glycolipids 1601 7.1 Glycolipids: Occurrence, Significance, and Properties 1603 Otto Hoist 7.2 Synthesis of Glycolipids 1629 Masahiro Wakao, Yasuo Suda 7.3 Gangliosides in the Nervous System: Biosynthesis and Degradation 1671 Robert K. Yu, Toshio Ariga, Makoto Yanagisawa, Guichao Zeng 7.4 Chemical Synthesis of Glycosylphosphatidylinositol (GPI) Anchors and GPI-Linked Structures 1697 Zhongwu Guo, Lee Bishop 8 Glycoproteins 1733 8.1 Glycoproteins: Occurrence and Significance 1735 Valentin Wittmann 8.2 Glycoproteins: Properties 1771 Valentin Wittmann Table of Contents XIII 8.3 Biologically Relevant Glycopeptides: Synthesis and Applications 1795 Clay S. Bennett, Richard J. Payne, Kathryn M. Koeller, Chi-Huey Wong 8.4 Glycosylation Engineering of Glycoproteins 1859 Reiko Sadamoto, Shin-Ichiro Nishimura 8.5 Glycoprotein Analysis 1873 Daryl Fernandes, Daniel Spencer Volume 3. 9 Glycomimetics 1885 9.1 Azaglycomimetics: Natural Occurrence, Biological Activity, and Application 1887 Naoki Asano 9.2 Carbasugars: Synthesis and Functions 1913 Yoshiyuki Kobayashi 9.3 Sulfur-Containing Glycomimetics 1999 Andreas Steiner, Arnold Stiitz, Tanja Wrodnigg 9.4 C-Glycosyl Analogs of Oligosaccharides 2021 Boris Vauzeilles, Dominique Urban, Gilles Doisneau, Jean-Marie Beau 9.5 Oligosaccharide Mimetics 2079 Hans Peter Wessel, Susana Dias Lucas 10 Key Technologies and Tools for Functional Glycobiology . .2113 10.1 Key Technologies and Tools for Functional Glycobiology: Introduction 2115 Shin-Ichiro Nishimura 10.2 Microarrays - A Key Technology for Glycobiology 2121 Yan Liu, Ten Feizi 10.3 Non-Natural Sugar Analogues: Chemical Probes for Metabolic Oligosaccharide Engineering . 2133 Udavanath Aich, Kevin J. Yarema XIV Table of Contents 10.4 Glycomics and Mass Spectrometry 2191 Anne Dell, Jihye Jang-Lee, Poh-Choo Pang, Simon Parry, Mark Sutton-Smith, Berangere Tissot, Howard R. Morris, Maria Panico, Stuart M. Haslam 10.5 Informatics Tools for Glycomics: Assisted Interpretation and Annotation of Mass Spectra 2219 Alessio Ceroni, Hiren J. Joshi, Kai Maafi, Rene Ranzinger, Claus-W. von der Lieth? 11 Biosynthesis and Degradation 2241 11.1 Biosynthesis and Degradation of Mono-, Oligo-, and Polysaccharides: Introduction 2243 Iain B. H. Wilson 11.2 Molecular Basis for the Biosynthesis of Oligo- and Polysaccharides 2265 Iain B. H. Wilson, Christelle Breton, Anne Imberty, Igor Tvaroska 11.3 Polysaccharide Degradation 2325 Bruce A. Stone, Birte Svensson, Michelle E. Collins, Robert A. Rastall 12 Glycomedicine 2377 12.1 Novel Approaches for Glycodrug Discovery 2379 Hirosato Kondo 12.2 Biomedicine of Monosaccharides 2399 Helen M. I. Osborn, Philip G. Evans, Karel Bezouska 12.3 Structure and Function of Mammalian Carbohydrate-Lectin Interactions 2445 Kevin Anderson, David Evers, Kevin G. Rice 12.4 Multivalency in Protein-Carbohydrate Recognition 2483 Laura L. Kiessling, Travis Young, Todd D. Gruber, Kathleen H. Mortell 12.5 Biomedicine of Enkephalin-Derived Glycopeptide Analgesics . 2525 Robin Poll 12.6 Antitumor and Antimicrobial Glycoconjugates 2545 Thisbe K. Lindhorst 12.7 Glycoside vs. Aglycon: The Role of Glycosidic Residue in Biological Activity 2589 Vladimir Kfen Table of Contents XV 12.8 Mucin-Based Vaccines 2645 Jonathan P. Richardson, Derek Macmillan 12.9 Polysaccharide-Based Vaccines 2699 Violeta Fernandez Santana, Yury Valdes Balbin, Janoi Chang Calderon, Luis Pena Icart, Vicente Verez-Bencomo Appendix: Nomenclature of Carbohydrates 2725 Index 2839 1.1 Structure and Conformation of Carbohydrates T. Bruce Grindley Department of Chemistry, Dalhousie University, Halifax, NS B3H 4J3, Canada [email protected] 1 Conformational Analysis 4 1.1 Introduction 4 1.2 Conformations of Cycloalkanes and Heterocycles 5 1.2.1 Conformations of Cyclohexanes 5 1.2.2 Conformations of Tetrahydropyran Derivatives 7 1.2.3 Conformations of Cyclopentanes and Tetrahydrofurans 11 1.3 Conformations of Monosaccharides 13 1.3.1 Conformations of Acyclic Carbohydrates 13 1.3.2 Conformations of Pyranoses 15 1.3.3 Conformations of Furanoses 28 1.3.4 Conformations of Septanoses 30 1.4 Conformations of Disaccharides, Trisaccharides, and Oligosaccharides 32 1.4.1 Conformations of Disaccharides 32 1.4.2 Conformations of Trisaccharides and Oligosaccharides 36 2 Physical Methods 37 2.1 Introduction 37 2.2 X-Ray Crystallography 37 2.3 NMR Spectroscopy 37 2.3.1 Chemical Shifts 38 2.3.2 Scalar Coupling 38 2.3.3 Dipolar Coupling 40 2.3.4 Nuclear Overhauser Effect 40 2.4 Circular Dichroism and Optical Rotatory Dispersion 42 2.5 Molecular Modeling 42 1.2 General Properties, Occurrence, and Preparation of Carbohydrates John F. Robyt Laboratory of Carbohydrate Chemistry and Enzymology, Department of Biochemistry, Biophysics, and Molecular Biology, 4252 Molecular Biology Building, Iowa State University, Ames, IA 50011, USA jrobyt @ iastate.edu 1 General Properties and Occurrence of Carbohydrates 60 2 Carbohydrate Property of Optical Rotation of Plane Polarized Light 60 3 The Structures of Carbohydrates 61 3.1 The Simplest Carbohydrates 61 3.2 Analogues of D-Glyceraldehyde 62 3.3 The Formation of Carbohydrates Containing More than Three Carbons 62 3.4 Special Properties of Pentoses and Hexoses 63 3.5 D-Glucose: the Most Prominent Carbohydrate on the Earth 64 3.6 Occurrence of D-Erythrose, D-Ribose, and D-Xylose 66 3.7 Occurrence of Hexoses 68 4 Properties and Occurrence of D-Glucose 68 4.1 D-Glucose in the Free State 68 4.2 D-Glucose in the Combined State 68 4.2.1 Occurrence of D-Glucose Combined with D-Fructose, D-Galactose, and D-Glucose, and High-Energy D-Glucose Donors 69 4.2.2 Properties and Occurrence of Sucrose and Sucrose Oligosaccharides Containing D-Galactose 69 4.2.3 Properties and Occurrence of D-Glucose Combined with D-Galactose to Give Lactose and Higher Oligosaccharides 71 4.2.4 Properties and Occurrence of a-D-Glucose Combined with a-D-Glucose to Give a,a-Trehalose 72 5 Properties and Occurrence of D-Glucose in Polysaccharides and Cyclodextrins 72 5.1 Properties and Occurrence of Starch 72 5.2 Properties and Occurrence of Glycogen 74 5.3 Properties and Occurrence of Dextrans, Alternan, Mutan, and Pullulan 74 5.4 Properties and Occurrence of D-Glucose in Cyclic Dextrins 75 5.5 Properties and Occurrence of Cellulose 76 58 General Principles