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Foreword xvii Preface xix 1 Protecting Group Strategies in Carbohydrate Chemistry 1 Anne G. Volbeda, Gijs A. van der Marel, and Jeroen D. C. Codée
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 Donnier Maréchal, Sébastien 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 Sébastien 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 Sébastien 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 N protecting Groups for 2Amino2deoxyglycosides 169 Sébastien 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 Jean Marie Beau, Yann Bourdreux, Guillaume Despras, Alexandra Gouasmat, Géraldine 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. O''Doherty
9.1 Introduction 243
9.2 Atomless Protecting Groups 244
9.3 De Novo Approach to Carbohydrates 244
9.4 O''Doherty Approach to Carbohydrates 246
9.5 Conclusion 273
9.6 Experimentals [3] 273 Abbreviations 278 References 279 10 Protecting Group Strategies for Sialic Acid Derivatives 283 Harsha Amarasekara, Szymon Buda, Appi R. Mandhapati, and David Crich 10.1 Introduction 283
10.2 Protection of the Carboxylate Group 283
10.3 Protection of Amine Function 289
10.4 Selective Protection of Alcohols 294
10.5 Access to Protected Sialic Acid Derivatives by Total Synthesis 301
10.6 Access to Protected Sialic Acid Derivatives by Chemoenzymatic Synthesis 301
10.7 Preparation of Methyl (methyl 5acetamido3,5dideoxydglyceroβdgalactonon2ulopyranosid)onate [20, 22, 104] 301 Abbreviations 302 References 302 11 Strategies Toward Protection of 1,2 and 1,3Diols in Carbohydrate Chemistry 307 Marie Schuler and Arnaud Tatibouët
11.1 Introduction 307
11.2 Protection as Cyclic Acetals 307
11.3 Protection as Orthoesters 320
11.4 Silylene Acetals as Protecting Groups 324
11.5 Cyclic Carbonate 327
11.6 Summary and Conclusions 329
11.7 Experimental
Part: Procedure for Regioselective and Reductive Benzylidene Opening Synthesis of Methyl 2,3,4TriObenzylαdglucopyranoside 329 Abbreviations 329 References 330 12 Protecting Group Strategies Toward Glycofuranoses 337 Vincent Ferrières, Laurent Legentil, and Loïc Lemiègre
12.1 Introduction 337
12.2 What About Chemistry Without Protecting Groups? 338
12.3 Protecting Group Interconversion 353
12.4 Multistep Synthesis of Some Furanosylcontaining Glycosides and Conjugates 358
12.5 The Striking Ring Contraction Strategy 362
12.6 Conclusion Strategy for Synthesizing 4Amino4deoxy and 4Deoxy4thioaldose Derivatives 364 Abbreviations 364 References 366 13 Cyclodextrin Chemistry via Selective Protecting Group Manipulations 371 Juan M. Benito and José M. García Fernández
13.1 Introduction 371
13.2 PerOprotection of Cyclodextrins 373
13.3 Faceselective Differentiation: Primary vs Secondary Hydroxyl Protection 374
13.4 Single Hydroxyl Protection Strategies 379
13.5 Concerted Protection of Hydroxyl Sets (Pairs or Triads) 381
13.6 Regioselective Deprotection of Symmetric Cyclodextrins 384
13.7 Summary and Conclusions 388
13.8 Experimental Procedures 388 Abbreviations 389 References 390 14 Protecting Group Strategies Toward Sulfated Glycosaminoglycans 395 Hélène Ledru, Pascal Matton, Jean Maurice Mallet, and Chrystel Lopin Bon
14.1 Introduction 395
14.2 O and Nsulfation in Glycosaminoglycan Glycosaminoglycans Synthesis 397
14.3 Protecting Group Strategies for the Synthesis of Sulfated Oligosaccharides of the Proteoglycans Linkage Region 397
14.4 Protecting Group Strategy for the Synthesis of Chondroitin Sulfate 403
14.5 Protecting Groups in Heparin and HS Synthesis 415
14.6 Summary and Conclusions 419
14.7 Experimental
Part: Procedure for Regioselective 6Obenzoylation Followed by 4Sulfation, an Example of the Synthesis of Disaccharide 31 [18] 419 Abbreviations 420 References 421 15 Applications of Fluorous and Ionic Liquid Tags in Oligosaccharide Synthesis 423 Imke Sittel and M. Carmen Galan
15.1 Introduction 423
15.2 Fluorous Supports 424
15.3 Ionic Liquid Supports 436
15.4 Conclusions 447 Abbreviations 447 References 448 16 Orthogonally Protected Building Blocks for Automated Glycan Assembly 451 Fabian Pfrengle and Peter H. Seeberger
16.1 Introduction 451
16.2 Protecting Groups 452
16.3 General Strategy for the Design of Orthogonally Protected Building Blocks 460
16.4 "Approved Building Blocks" for Automated Glycan Assembly 461
16.5 Solidphase Syntheses of Mammalian, Microbial, and Plant Oligosaccharides 464
16.6 Chances, Challenges, and Commercialization of Automated Glycan Assembly 467 Abbreviations 469 References 470 17 Kilogramscale Production of Synthetic Heparin Analogs: Some Chemical Considerations 473 Patrick Trouilleux, Pierre Potier, and Pierre Alexandre Driguez
17.1 Introduction 473
17.2 Kilogram Synthesis of Heparin Building Blocks 474
17.3 Experimental Section 487
17.4 Summary and Conclusions 489 Abbreviations 489 References 490 Index 493<