Synthesis and Characterization of Glycosides

Preface to the Third Edition
Preface to the Second Edition
Preface to the First Edition
Contents
1 Glycosides, Synthesis and Characterization
	1.1 Introduction
	1.2 Reactions of Monosaccharides
	1.3 Chemical Modifications
		1.3.1 Oxidations
		1.3.2 Periodate Oxidation
		1.3.3 Tollens Reaction
		1.3.4 Benedict and Fehling Test
		1.3.5 Nucleophilic Addition
		1.3.6 Enediol Rearrangement
		1.3.7 Kiliani-Fischer Synthesis
		1.3.8 The Ruff Degradation
		1.3.9 Conversion to Furfural Derivatives
	1.4 Biosynthesis of Sugars
		1.4.1 Sugars as Energy Sources
	1.5 Synthesis of Carbohydrates
		1.5.1 Chemical Synthesis
		1.5.2 C-Glycosyl Amino Acids
		1.5.3 Enzymatic Synthesis
		1.5.4 Chemoenzymatic Synthesis
	1.6 Synthesis of Carbohydrates Mimetics
		1.6.1 Iminosugars
		1.6.2 Aminosugars
		1.6.3 Thiopyranoside Monosaccharides
		1.6.4 Carbapyranoside-Saccharides
	1.7 Glycoside Reactivity
	1.8 The Leaving Groups
	1.9 Glycosyl Donors
		1.9.1 Glycosyl Halides
	1.10 Protecting Groups
	1.11 Selective Protections (Scheme 1.107)
	1.12 Selective Deprotections (Scheme 1.108)
	References
2 O-Glycoside Formation
	2.1 General Methods
		2.1.1 The Michael Reaction
		2.1.2 The Fischer Reaction
		2.1.3 The Koenigs-Knorr Reaction
		2.1.4 The Helferich Reaction
		2.1.5 Acetate Donors
		2.1.6 The Imidate Reaction
		2.1.7 The Sulfur Reaction
		2.1.8 Unprotected Glycosylations
		2.1.9 The Armed-Disarmed Method
		2.1.10 The Glycal Reaction
		2.1.11 Phenyl Alkynyl Donors
		2.1.12 Fluorine Reaction
		2.1.13 Iodine Reaction
		2.1.14 Silyl Reaction
		2.1.15 Phosphate Reaction
		2.1.16 The Pool Strategy
		2.1.17 Enzymatic Approach
		2.1.18 The Solid Phase Methodology
		2.1.19 Miscellaneous Glycosylations
		2.1.20 Heterogenous Catalysis
		2.1.21 Photoactivated Glycosylation Reactions
		2.1.22 Mechanochemistry for Glycosylation Reactions
		2.1.23 Electrochemical Glycosylation Reactions
		2.1.24 Synthesis of Oligosaccharides and Cyclic Oligosaccharides
	References
3 N-Glycosides
	3.1 Nucleoside Formation
	3.2 Protecting Groups
		3.2.1 Ribofuranoside Protecting Groups
	3.3 General Methods
		3.3.1 The Michael Reaction
		3.3.2 The Fischer-Helferich Reaction
		3.3.3 The Davol-Lowy Reaction
		3.3.4 Silyl Coupling Reaction
		3.3.5 Sulfur Mediated Reaction
		3.3.6 Imidate Mediated Reaction
		3.3.7 Mitsunobu Reaction
		3.3.8 Palladium Mediated Reaction
		3.3.9 Ortho-Alkynylbenzoates Protocol
		3.3.10 Microbial/Enzymatic Approach
	3.4 Oligonucleotide Synthesis
		3.4.1 Phosphoramidite Method
		3.4.2 HOBt Solid Phase Synthesis
		3.4.3 Phosphonate Method
		3.4.4 Phosphorimidazolides Method
		3.4.5 Modified Oligonucleotides
	References
4 Nucleoside Mimetics
	4.1 Modified N-Nucleosides
		4.1.1 Heterocycle Modifications
		4.1.2 Sugar Modifications
		4.1.3 Complex Nucleosides
	4.2 C-Nucleosides
	4.3 Carbocyclic Nucleosides
		4.3.1 Cyclopropane Carbocyclic Nucleosides
		4.3.2 Cyclobutane Carbocyclic Nucleosides
		4.3.3 Cyclopentane Carbocyclic Nucleosides
		4.3.4 Palladium Mediated
		4.3.5 Enzymatic Synthesis
		4.3.6 Carbocyclic C-Nucleosides
	4.4 Acyclic Nucleosides
	4.5 Thionucleosides
		4.5.1 Preparation of Thioribofuranosyl Intermediates
		4.5.2 Glycosidic Bond Formation
	References
5 C-Glycosides
	5.1 Synthetic Approaches for the Preparation of C-Glycosides
		5.1.1 Electrophilic Glycosyl Donors
		5.1.2 Concerted Reaction and Ring Formation
		5.1.3 Palladium Mediated Reactions
		5.1.4 Mitsunobu Reaction
		5.1.5 Nucleophilic Sugars
		5.1.6 Cross-Metathesis Reaction
		5.1.7 Samarium Promoted Reaction
		5.1.8 The Ramberg-Bäcklund Reaction
		5.1.9 Free Radical Approach
		5.1.10 Exoglycals
		5.1.11 The Tether Approach
		5.1.12 Unprotected Sugars
		5.1.13 Enzymatic Approach
	References
6 Glycoconjugates
	6.1 Biological Function and Structural Information
		6.1.1 Classification of Glycocoproteins
		6.1.2 Recognition Sites
		6.1.3 Structural Information of Glycoproteins
	6.2 Carbohydrate Binding Proteins
		6.2.1 Combining Sites
	6.3 Glycopeptide Synthesis
	6.4 Glycoprotein Synthesis
		6.4.1 Indiscriminate Glycosylation
		6.4.2 Chemoselective and Site-Specific Glycosylation
		6.4.3 Native Chemical Ligation and Site-Selective Glycosylation
		6.4.4 Lansbury Aspartylation
		6.4.5 Guanylation Reaction
		6.4.6 Enzymatic Synthesis
	6.5 Synthesis of Antigenic Glycoconjugates
		6.5.1 Glycosphingolipid and Gangliosides
	6.6 Glycopeptoids
	6.7 Glycoproteins
	6.8 Synthetic Vaccines
	References
7 Hydrolysis of Glycosides
	7.1 Acidic Hydrolysis
	7.2 Basic Hydrolysis
		7.2.1 Phenolic Glycosides
		7.2.2 Enolic Glycosides
		7.2.3 β-Susbstituted Alcohol Glycosides
	7.3 Enzymatic Hydrolysis
		7.3.1 α-Glucosidases
		7.3.2 β-Glucosidases
		7.3.3 β-Glucanasas, β-Quitinases
		7.3.4 β-Cellulase
		7.3.5 β-Glucuronidase
		7.3.6 Retaining Versus Inverting Glucosidases
		7.3.7 Glycosidase Enzymatic Activity Detection
		7.3.8 Β-1,4-Glucanases
		7.3.9 Fluorescent O-Glycosides
		7.3.10 O-Glycosides Measured by Absorption
		7.3.11 Histochemical O-Glycosides
	References
8 Nuclear Magnetic Resonance of Glycosides
	8.1 NMR of Glycosides
	8.2 NMR of N-glycosides
	References
9 X-Ray Diffraction of Glycosides
	9.1 X-Ray Diffraction of O-Glycosides
	9.2 X-Ray Diffraction of Nucleosides
	References
10 Mass Spectrometry of Glycosides
	10.1 FAB Fragmentation Patters
	10.2 The Domon-Costello Fragmentation
	References
Index