Protecting Groups: Strategies and Applications in Carbohydrate Chemistry

?Protecting Groups: Strategies and Applications in Carbohydrate Chemistry draws together several decades of advances in selectively protecting specific positions of carbohydrates and then takes a fresh look at this area from the perspective of synthetic strategies. (?) Throughout the book, the authors present useful examples of reliable experimental methods for introduction and removal of the most important protecting groups. (?) It is therefore highly suitable for newcomers to the field and for experienced glycochemists or glycobiologists who would like to expand their knowledge of this challenging field. In short, this is a book that should occupy the shelves of every practicing and aspiring carbohydrate chemist.? Carolyn R. Bertozzi in Angew. Chem. Int. Ed. 2019, 58, 2

Sbastien Vidal, PhD, holds a CNRS position at the University of Lyon, France. His main area of research is the design of glycoclusters for anti-adhesive strategy against bacterial infections and enzyme inhibitors targeting glycogen phosphorylase with applications in type-2 diabetes. In 2014, he was given the young investigator award "Prix du Groupe Franais des Glycosciences".

Foreword xvii Preface xix 1 Protecting Group Strategies in Carbohydrate Chemistry 1 Anne G. Volbeda, Gijs A. van der Marel, and Jeroen D. C. Code 1.1 Discriminating Different Functionalities on a Carbohydrate Ring 1 1.2 Strategies for an (Oligo)saccharide Synthesis Campaign 5 1.3 Reactivity and Stereochemistry 7 1.4 Protecting Groups in Automated Synthesis 14 1.5 Summary and Outlook 20 Abbreviations 23 References 24 2 Protecting Groups at the Primary Position of Carbohydrates 29 Marion DonnierMarchal, Sbastien Vidal, and Michele Fiore 2.1 Introduction 29 2.2 Selective Primary Hydroxyl Group Protection 30 2.3 Selective Primary Hydroxyl Group Deprotection 45 2.4 Regioselective Transformations at the Primary Position 53 2.5 Summary and Conclusions 59 2.6 Experimental Section 59 Abbreviations 60 References 61 3 Protecting Groups at the Secondary Positions of Carbohydrates 69 Sbastien Vidal and Peter G. Goekjian 3.1 Introduction 69 3.2 The Major Protecting Group Motifs 72 3.3 Conclusion 95 3.4 Experimental Section 95 Abbreviations 96 References 97 4 Regioselective Protection at the Secondary Positions of Carbohydrates with Acyclic Protecting Groups 109 Peter G. Goekjian and Sbastien Vidal 4.1 Introduction 109 4.2 Regioselective Protections at the 2Position 110 4.3 Regioselective Protections at the 3Position 122 4.4 Regioselective Protections at the 4Position 130 4.5 Regioselective bisProtection of the 2,6, 3,6, and 4,6Positions of Hexopyranoside Tetraols 130 4.6 Regioselective Monodeprotection of Peracetyl and Perbenzyl Monosaccharides 134 4.7 Summary and Conclusions 135 4.8 Experimental Section 136 Abbreviations 137 References 138 5 Protecting Groups at the Anomeric Position of Carbohydrates 145 Chadamas Sakonsinsiri and W. Bruce Turnbull 5.1 Introduction 145 5.2 Oalkyl and Oaryl Glycosides 146 5.3 Glycosyl Esters 151 5.4 Cyclic Acetals, Ketals, and Orthoesters 155 5.5 Silyl Ethers 157 5.6 Sglycosyl and Nglycosyl Derivatives 158 5.7 Concluding Remarks 162 5.8 Example Experimental Procedures 164 Abbreviations 165 References 166 6 Nprotecting Groups for 2Amino2deoxyglycosides 169 Sbastien Vidal 6.1 Introduction 169 6.2 Nacylbased Protecting Groups 171 6.3 Imidobased Protecting Groups 175 6.4 Carbamatebased Protecting Groups 179 6.5 Imine or Enaminebased Protecting Groups 185 6.6 2Deoxy2azido Derivatives as a Protecting Group 187 6.7 From Glycals to 2Azido Intermediates 188 6.8 From Glycals to 2Sulfonamido Intermediates 190 6.9 Summary and Conclusions 191 6.10 Experimental Section 191 Abbreviations 192 References 193 7 Onepot Multistep Regioselective Protection of Carbohydrates Catalyzed by Acids 201 JeanMarie Beau, Yann Bourdreux, Guillaume Despras, Alexandra Gouasmat, Graldine San Jose, Dominique Urban, and Boris Vauzeilles 7.1 Introduction 201 7.2 Examples of Early Developments of the Onepot Multistep Regioselective Hydroxyl Protection of Carbohydrates 202 7.3 Onepot Multistep Methods from Silylated Substrates 204 7.4 Onepot Multistep Methods Catalyzed by Copper Triflate on Unprotected Sugars 216 7.5 Other Onepot Multistep Methods Catalyzed by Acids 216 7.6 Conclusions and Outlook 220 7.7 Experimental Procedures 220 Acknowledgments 221 Abbreviations 222 References 222 8 Acyl Migrations in Carbohydrate Chemistry 227 Filip S. Ekholm and Reko Leino 8.1 Introduction 227 8.2 Mechanism and Migration Kinetics 228 8.3 Acyl Group Migration Synthetic Applications 230 8.4 Summary and Conclusions 238 8.5 Selected Experimental Procedures 239 Abbreviations 239 References 240 9 De Novo Asymmetric Synthesis of Oligosaccharides Using Atomless Protecting Groups 243 Debarpita Ray and George A. ODoherty 9.1 Introduction 243 9.2 Atomless Protecting Groups 244