Front Cover

Advances in Carbohydrate Chemistry and Biochemistry

Copyright

Contents

Contributors

Preface

Chapter One: Stevia Glycosides: Chemical and Enzymatic Modifications of Their Carbohydrate Moieties to Improve the Sweet- ...

1. Introduction

2. Steviol Glycoside Structures from S. rebaudiana

3. Steviol Variants of Glycoside Structures from S. rebaudiana

4. Stability of Steviol Glycosides

5. Structure-Sweetness Relationship

6. Chemical Modifications of Steviol Glycosides

7. Enzymatic Modifications of Steviol Glycosides

7.1. Cyclodextrin Glycosyl Transferase Systems

7.2. α-Glucosidase Transglycosylation Systems

7.3. β-Glucosidase Transglycosylation and Deglycosylation Systems

7.4. α-Galactosidase Transglycosylation Systems

7.5. β-Galactosidase Transglycosylation Systems

7.6. β-Fructosidase Transglycosylation Systems

7.7. β-Glycosyltransferase Glycosylation Systems Using UDP-Sugars

8. Patents Regarding Enzymatic Modifications of Steviol Glycosides

9. Concluding Remarks

Addendum

Acknowledgments

References

Chapter Two: Endoglycosidases for the Synthesis of Polysaccharides and Glycoconjugates

1. Introduction

1.1. Biological Functions of Glycans and Glycoconjugates

1.2. Synthetic Glycans and Glycoconjugates for Deciphering Functions

1.3. Enzymes as a Tool for the Synthesis of Glycans and Glycoconjugates

2. Endoglycosidases in the Synthesis of Natural and Artificial Polysaccharides

2.1. Synthesis of Artificial Cellulose and Derivatives via Enzymatic Polymerization of Glycosyl Fluorides Catalyzed by Ce ...

2.2. Chitinase-Catalyzed Synthesis of Artificial Chitin and Derivatives Using Sugar Oxazolines as Activated Substrates

2.3. Hyaluronidase-Catalyzed Construction of Glycosaminoglycans Using Sugar Oxazoline as the Activated Substrates

2.4. Endo-β-Xylosidase-Catalyzed Transglycosylation in the Synthesis of Proteoglycans

3. Endoglycosidases in the Synthesis of N-Glycopeptides and N-Glycoproteins

3.1. Exploration of Glycan Oxazolines as Donor Substrates for ENGase-Catalyzed Synthesis of Complex Glycopeptides and Gly ...

3.2. Generation of ENGase-Based Glycosynthases for Transglycosylation

3.3. ENGase-Catalyzed Synthesis of Selected Biologically Interesting Glycopeptides and Glycoproteins

3.4. ENGase-Catalyzed Transglycosylation for Glycosylation Remodeling of Therapeutic Monoclonal Antibodies

4. Endoglycosidases for the Synthesis of Neoglycolipids and Glycosphingolipids

4.1. Ceramide Glycanase-Catalyzed Transglycosylation for Glycolipid Synthesis

4.2. Endoglycoceramidase-Based Glycosynthase for the Synthesis of Glycosphingolipids

5. Concluding Remarks

Acknowledgment

References

Chapter Three: Recent Advances Toward Robust N-Protecting Groups for Glucosamine as Required for Glycosylation Strategies

1. Introduction

2. The Glycosylation Reaction

3. Acyclic N-Protecting Groups

3.1. The Acetyl (Ac) Group

3.2. The Diacetyl [-N(Ac)2] Group

3.3. The Chloroacetyl (ClCH2CO) Group

3.4. The Dichloroacetyl Group

3.5. The Trichloroacetyl (TCA) and Trifluoroacetyl (TFA) Groups

3.6. The Pent-4-enoyl Group

3.7. The Trichloroethoxycarbonyl (Teoc) Group

3.8. The 2,2,2-Trichloro-1,1-dimethylethyloxycarbonyl (TCBOC) Group

3.9. The Allyloxycarbonyl (AOC) Group

3.10. The Benzyloxycarbonyl (Cbz or Z) Group

3.11. The p-Nitrobenzyloxycarbonyl (PNZ) Group

3.12. The Methoxycarbonyl Group

3.13. The Ethoxycarbonyl, Chloroethyloxycarbonyl, and Phenyloxycarbonyl Groups

3.14. The (1,3-Dimethyl-2,4,6-(1H,3H,5H)-trioxopyrimidin-5-ylidene)methyl (DTPM) Group

3.15. The 4,4-Dimethyl-2,6-dioxocyclohexylidenemethyl (Dde) Group

3.16. The N-2,4-Dinitrophenyl (DNP) Group

3.17. The Diphenylphosphoryl (DPPO) and Dimethylphosphoryl (DMPO) Groups

3.18. The N-Alkylacetamido Groups

3.19. Fluorous-Protecting Groups (Froc)

4. Cyclic N-Protecting Groups

4.1. Oxazolines

4.1.1. Methyloxazoline

4.1.2. Phenyloxazoline

4.1.3. 2-Alkoxy Glyco-[2,1-d]-2-oxazolines

4.2. Nonparticipating Groups

4.2.1. The 2,3-Oxazolidinone Group

4.2.2. The 2,5-Dimethylpyrrole Group (DMP)

4.3. Participating Groups

4.3.1. Five-Membered Ring Groups

4.3.1.1. The Phthalimido Family

4.3.1.2. The Dithiasuccinyl Group (Dts)

4.3.1.3. The Dimethylmaleoyl (DMM) Group

4.3.1.3.1. Formation of β Glycosides

4.3.1.3.2. Transformation of N-DMM to NHAc

4.3.1.3.3. β-(1→4)-Mannosyl-Linked Chitobiose-Type Compounds

4.3.1.3.4. Glycolipid Synthesis

4.3.1.3.5. Glycosaminoglycan (GAG) Syntheses

4.3.1.3.6. N-DMM-Protected Glycosyl Iodides

4.3.1.3.7. N-DMM-Based Synthesis of Trehalosamines

4.3.1.3.8. Synthesis of Chitooligomers

4.3.1.3.9. Synthesis of Murin-Type Oligosaccharides

4.3.1.3.10. N-Glycan Syntheses

4.3.1.3.11. Human Milk Oligosaccharides (HMOs)

4.3.1.3.12. Galactofuranosyl-β-(1→4)-GlcNAc

4.3.1.3.13. Glycosylation of 3- and 4-OH-Free DMM-Protected d-Glucosamines and d-Allosamines

4.3.1.3.14. Solid-Phase Synthesis of N-Glycans and HMOs

4.3.1.4. The Diphenylmaleoyl (DPM) Group

4.3.2. Six-Membered Ring Groups

4.3.2.1. The Thiodiglycolyl (TDG) Group

4.3.2.2. The Dimethylglutaroyl (DMG) Group

4.3.2.3. The Diglycolyl (DG) Group

5. Latent Amino-Protecting Groups

5.1. The Azido Glycosylation Method

5.2. 2-Nitro Sugars

5.2.1. 2-Nitro Glycals

5.2.1.1. O-Glycosides via Michael-Type Addition

5.2.1.2. Synthesis of N-Nucleosides

5.2.1.3. Synthesis of Glycosyl Phosphonates

5.2.1.4. Synthesis of β-C-Glycosyl Compounds (``β-C-Glycosides´´)

5.2.2. 2-Nitro-1-thioglycosyl Donors

6. Conclusions

Acknowledgments

References

Chapter Four: Carbohydrate-Processing Enzymes of the Lysosome: Diseases Caused by Misfolded Mutants and Sugar Mimetics as ...

1. Introduction

2. Carbohydrate-Processing Enzymes of the Glycosphingolipid Degradation Pathway

2.1. Lysosomal β-d-Galactosidase

2.2. Lysosomal N-Acetyl-β-d-hexosaminidase

2.3. Lysosomal α-d-Galactosidase

2.4. Arylsulfatase A

2.5. Lysosomal β-d-Galactocerebrosidase

3. Lysosomal Glycogen Degradation and Glycogen Storage Disease

3.1. Lysosomal α-d-Glucosidase

4. Enzymes of the Glycoprotein Degradation Pathway and Glycoproteinoses

4.1. Lysosomal α-l-Fucosidase

4.2. Neuraminidase 1

4.3. N-Acetyl-α-d-galactosaminidase

4.4. Lysosomal α-d-Mannosidase

4.5. Lysosomal β-d-Mannosidase

4.6. Aspartyl-N-acetyl-d-glucosaminidase

5. Enzymes Involved in Mucopolysaccharide Degradation and Mucopolysaccharidoses

5.1. Lysosomal α-l-Iduronidase

5.2. Lysosomal Heparan-N-sulfatase

5.3. Lysosomal N-Acetyl-α-d-glucosaminidase

5.4. Heparin Acetyl-CoA:α-d-glucosaminide-N-acetyltransferase

5.5. Lysosomal N-Acetyl-d-glucosamine-6-sulfatase

5.6. Lysosomal N-Acetyl-d-galactosamine-6-sulfatase

5.7. N-Acetyl-d-galactosamine-4-sulfatase (Arylsulfatase B)

5.8. Lysosomal β-Glucuronidase

5.9. Lysosomal Hyaluronidase

6. Conclusions and Outlook

References

Author Index

Subject Index

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