Cover

Title Page

Copyright

Contents

List of Contributors

Preface

Part I Introduction

Chapter 1 Stereoselective Glycosylations – Additions to Oxocarbenium Ions

1.1 Introduction

1.2 Stability, Reactivity, and Conformational Behavior of Glycosyl Oxocarbenium Ions

1.3 Computational Studies

1.4 Observation of Glycosyl Oxocarbenium Ions by NMR Spectroscopy

1.5 Oxocarbenium Ion(-like) Intermediates as Product-Forming Intermediates in Glycosylation Reactions

1.6 Conclusion

References

Chapter 2 Application of Armed, Disarmed, Superarmed, and Superdisarmed Building Blocks in Stereocontrolled Glycosylation and Expeditious Oligosaccharide Synthesis

2.1 Introduction: Chemical Synthesis of Glycosides and Oligosaccharides

2.2 Fraser‐Reid’s Armed–Disarmed Strategy for Oligosaccharide Synthesis

2.3 Many Reactivity Levels Exist between the Armed and Disarmed Building Blocks

2.4 Modes for Enhancing the Reactivity: Superarmed Building Blocks

2.5 Modes for Decreasing the Reactivity: Superdisarmed Building Blocks

2.6 Application of Armed and Disarmed Building Blocks in Stereocontrolled Glycosylation

2.7 Application of Armed/Superarmed and Disarmed Building Blocks in Chemoselective Oligosaccharide Synthesis

2.8 Conclusions and Outlook

References

Chapter 3 Solvent Effect on Glycosylation

3.1 Introduction

3.2 General Properties of Solvents Used in Glycosylation

3.3 Polar and Noncoordinating Solvents in Glycosylation

3.4 Weakly Polar and Noncoordinating Solvents in Glycosylation

3.5 Polar and Coordinating Solvents in Glycosylation

3.6 Weakly Polar and Coordinating Solvents in Glycosylation

3.7 Solvent Effect of Ionic Liquid on Glycosylation

3.8 Solvent Effect on Electrochemical Glycosylation

3.9 Molecular Dynamics Simulations Studies on Solvent Effect

3.10 Conclusions

References

Part II Stereocontrolled Approaches to Glycan Synthesis

Chapter 4 Intramolecular Aglycon Delivery toward 1,2-cis Selective Glycosylation

4.1 Introduction

4.2 Ketal Type Tethers

4.3 Silicon Tethers

4.4 2-Iodoalkylidene Acetals as Tether

4.5 Benzylidene Acetals as Tether

4.6 IAD through Hemiaminal Ethers

4.7 Conclusions

References

Chapter 5 Chiral Auxiliaries in Stereoselective Glycosylation Reactions

5.1 Introduction

5.2 Neighboring Group Participation of O-2 Chiral Auxiliaries

5.3 Neighboring Group Participation of O-2 Achiral Auxiliaries

5.4 Preconfigured Chiral Auxiliaries

5.5 Conclusion

References

Chapter 6 Glycosylation with Glycosyl Sulfonates

6.1 Introduction

6.2 Formation of Glycosyl Sulfonates

6.3 Evidence for Glycosyl Sulfonates

6.4 Location of the Glycosyl Sulfonates in the General Glycosylation Mechanism

6.5 Applications in O-Glycoside Synthesis

6.6 Applications in S-Glycoside Synthesis

6.7 Applications in C-Glycoside Synthesis

6.8 Polymer-Supported Glycosylation with Sulfonates

6.9 Conclusion

References

Part III Catalytic Activation of Glycosides

Chapter 7 Stereoselective C-Glycosylation from Glycal Scaffolds

7.1 Introduction

7.2 Classification of C-Glycosylation Reactions

7.3 Ferrier-Type Rearrangement

7.4 Pd-Catalyzed Heck-Type

7.5 Tsuji–Trost-Type C-Glycosylation

7.6 Sigmatropic Rearrangement

7.7 NHC-Catalyzed C-Glycosylations

7.8 Conclusion

References

Chapter 8 Brønsted- and Lewis-Acid-Catalyzed Glycosylation

8.1 Introduction

8.2 Chiral Brønsted Acids

8.3 Achiral Brønsted Acids

8.4 Lewis-Acid-Catalyzed Glycosylations

8.5 Metals as Lewis Acids

8.6 Synthesis of C-Glycosides

8.7 Conclusions and Outlook

References

Chapter 9 Nickel-Catalyzed Stereoselective Formation of 1,2-cis-2-Aminoglycosides

9.1 Introduction

9.2 Biological Importance of 1,2-cis-Aminoglycosides

9.3 Use of Nonparticipatory Groups to Form 1,2-cis-Aminoglycosides

9.4 Nickel-Catalyzed Formation of 1,2-cis-Aminoglycosides

9.5 C(2)-N-Substituted Benzylidene Glycosyl Trichloroacetimidate Donors1

9.6 Studies of C(2)-N-Substituted Benzylideneamino Glycosyl N-Phenyl Trifluoroacetimidate Donors

9.7 1,2-cis-Amino Glycosylation of Thioglycoside Acceptors

9.8 Application to the Synthesis of Biologically Active Glycans

9.9 Conclusion

References

Chapter 10 Photochemical Glycosylation

10.1 Introduction

10.2 Photochemistry Basics

10.3 Photosensitized O-Glycosylation with Chalcogenoglycoside Donors

10.4 Photochemical O-Glycosylation with Other Donors

10.5 Photosensitized C-Glycosylation

10.6 Conclusions

References

Part IV Regioselective Functionalization of Monosaccharides

Chapter 11 Regioselective Glycosylation Methods

11.1 Introduction

11.2 Substrate Control: “Intrinsic” Differences in OH Group Reactivity of Glycosyl Acceptors

11.3 Substrate Control: Modulation of Acceptor OH Group Reactivity by Variation of Protective Groups

11.4 Substrate Control: Glycosyl Donor/Acceptor Matching in Regioselective Glycosylation

11.5 Reagent-Controlled, Regioselective Glycosylation

11.6 Enzyme-Catalyzed Regioselective Glycosylation

11.7 Synthetic Catalysts for Regioselective Glycosylation

11.8 Summary and Outlook

References

Chapter 12 Regioselective, One-Pot Functionalization of Carbohydrates

12.1 Introduction

12.2 Regioselective, Sequential Protection/Functionalization of Carbohydrate Polyols

12.3 Regioselective, One-Pot Protection of Sugars via TMS Protection of Polyols

12.4 Orthogonally Protected d-Glycosamine and Bacterial Rare Sugar Building Blocks via Sequential, One-Pot Nucleophilic Displacements of O-Triflates

12.5 Summary and Outlook

References

Part V Stereoselective Synthesis of Deoxy Sugars, Furanosides, and Glycoconjugate Sugars

Chapter 13 Selective Glycosylations with Deoxy Sugars

13.1 Introduction

13.2 Challenges in 2-Deoxy-Sugar Synthesis

13.3 Protecting Group Strategies

13.4 Addition to Glycals

13.5 Additions to Glycosyl Halides

13.6 Latent Glycosyl Halides

13.7 Reagent-Controlled Approaches

13.8 Umpolung Reactivity

13.9 Conclusion

References

Chapter 14 Selective Glycosylations with Furanosides

14.1 Introduction

14.2 Construction of the Furanose Template

14.3 Stereoselective Glycosylation with Furanoside Donors

14.4 Reactivity Tuning of Furanosides for Oligosaccharide Synthesis

14.5 Conclusion

References

Chapter 15 De novo Asymmetric Synthesis of Carbohydrate Natural Products

15.1 Introduction

15.2 Danishefsky Hetero-Diels–Alder Approach

15.3 MacMillan Proline Aldol Approach

15.4 The O’Doherty Approaches

15.5 Conclusion

References

Chapter 16 Chemical Synthesis of Sialosides

16.1 Introduction

16.2 Chemical Synthesis of Sialosides

16.3 Conclusions

References

Index

EULA