Domino and intramolecular rearrangement reactions as advanced synthetic methods in glycoscience / edited by Zbigniew J. Witczak, Roman Bielski. -- Hoboken, New Jersey : Wiley, c2016. – (58.17422/D671)

Contents

Foreword

Preface

Acknowledgments

List of Contributors

Abbreviations

1  Introduction to Asymmetric Domino Reactions                       1

1.1  Introduction, 1

1.2  Asymmetric Domino Reactions using Chiral Carbohydrate Derivatives, 3

1.3  Conclusions, 12

References, 13

2  Organocatalyzed Cascade Reaction in Carbohydrate Chemistry

2.1  Introduction, 16

2.2  C-Glycosides, 17

2.3  Amine-Catalyzed Knoevenagel-Additions, 20

2.4  Muiticomponent Reactions, 32

2.5  Amine-Catalyzed Cascade Reactions of Ketoses with 1,3-Dicarbonyl Compounds, 40

2.6  Conclusions, 44

References, 44

3  Reductive Ring-Opening in Domino Reactions of Carbohydrates       49

3.1  Introduction, 49

3.2  Bernet-Vasella Reaction, 50

3.3  Reductive Ring Contraction, 64

3.4  Conclusions, 73

References, 73

4  Domino Reactions Toward Carbohydrate Frameworks for Applications Across Biology and Medicine

4.1  Introduction, 76

4.2  Domino Reactions Toward Butenolides Fused to Six-Membered Ring Sugars and Thio Sugars, 77

4.3  Exploratory Chemistry for Amino Sugars' Domino Reactions, 80

4.4  Domino Reactions Toward Sugar Ring Contraction, 84

4.5  Macrocyclic Bislactone Synthesis via Domino Reaction, 91

4.6  Sugar Deoxygenation by Domino Reaction, 92

4.7  Conclusions, 94

References, 94

5  Multistep Transformations of BIS-Thioenol Ether-Containing Chirai Building Blocks: New Avenues in Glycochemistry

5.1  Introduction, 97

5.2  (5,6-Dihydro- 1,4-dithiin-2-yl)Methanol: Not Simply a Homologating Agent, 98

5.3  Sulfur-AsSisted Multistep Processes and Their Use in the De Novo Synthesis of Glycostructures, 101

5.4  Concluding Remarks, 111

5.5  Acknowledgments, 111

References, 111

6  Thio-Click and Domino Approach to Carbohydrate Heterocycles      114

6.1  Introduction, 114

6.2  Classification and Reaction Mechanism, 114

6.3  Conclusions, 119

References, 120

7  Convertible Isocyanides: Application in Small Molecule Synthesis, Carbohydrate Synthesis, and Drug Discovery                       121

7.1  Introduction, 121

7.2  Convertible Isocyanides, 125

7.3  Conclusions, 187

References, 187

8  Adding Additional Rings to the Carbohydrate Core: Access via (SPIRO) Annulation Domino Processes                            195

8.1   Introduction, 195

8.2   Spiroketals via a Domino Oxidation/Rearrangement Sequence, 196

8.3   Chromans and Isochromans via Domino Carbopalladation/Carbopalladation/Cyclization Sequence, 200

References, 208

9  Introduction to Rearrangement Reactions in Carbohydrate Chemistry

9.1   Introduction, 209

9.2   Classification, 210

9.3   Chapman Rearrangement, 211

9.4   Hofmann Rearrangement, 211

9.5   Cope Rearrangement, 211

9.6   Ferrier Rearrangement, 212

9.7   Claisen Rearrangement, 213

9.8   Overman Rearrangement, 214

9.9   Baeyer-Villiger Rearrangement, 215

9.10  Ring Contraction, 215

9.11  Conclusions, 216

References, 217

10 Rearrangement of a Carbohydrate Backbone Discovered "En Route" to Higher-Carbon Sugars                              219

10.1  Introduction, 219

10.2  Rearrangements Without Changing the Sugar Skeleton, 220

10.3  Rearrangements Connected with the Change of Sugar Unit(s), 221

10.4  Rearrangements Changing the Structure of a Sugar Skeleton, 224

10.5  Rearrangement of the Sugar Skeleton Discovered En Route to Higher-Carbon Sugars, 226

10.6  Conclusions, 237

Acknowledgments, 237

References, 237'

11 Novel Levoglucosenone Derivatives

11.1 Introduction, 240

11.2 Additions to the Double Bond of the Enone System Leading to the Formation of New Rings, 241

11.3 Reductions of the Carbonyl Group Followed by Various Reactions of the Formed Alcohol, 241

11.4 Functionalization of the Carbonyl Group by Forming Carbon-Nitrogen Double Bonds (Oximes, Enamines, Hydrazines), 242

11.5 Additions (But Not Cycloadditions) (Particularly Michael Additions) to the Double Bond of the Enone, 243

11.6 Enzymatic Reactions of Levoglucosenone, 244

11.7 High-Tonnage Products from Levoglucosenone, 244

11.8 Conclusions, 246

References, 247

12 The Preparation and Reactions of 3,6-Anhydro-v-Glycals            248

2.1  Introduction, 248

2.2  Preparation of 3,6-Anhydro-o-Glucal Under Reductive Conditions, 250

2.3  Addition Reactions of 3,6-Anhydro-D-Glucal, 251

2.4  Preparation of 6-O-Tosyl-D-Galactal and Reduction with Lithium Aluminum Hydride, 252

12.5  Conclusions, 254

References, 254

13 Ring Expansion Methodologies of Pyranosides to Septanosides and Structures of Septanosides                                      256

13.1  Introduction, 256

13.2  Synthesis of Septanosides, 258

13.3  Structure and Conformation of Septanosides, 269

13.4  Conclusions, 275

Acknowledgments, 276

References, 276

14 Rearrangements in Carbohydrate Templates to the Way to Peptide-Scaffold Hybrids and Functionalized Heterocycles           279

14.1  Introduction, 279

14.2  Synthesis of the Chiral Building Blocks: Applications of the Claisen-Johnson and Overman Rearrangements, 280

14.3  Peptide-Scaffold Hybrids, 282

14.4  Sequential Reactions for the Synthesis of Polyannular Heterocycles, 284

14.5  The First Total Synthesis of Amphorogynine C, 284

Acknowledgments, 293

References, 293

15 Palladium- and Nickel-Catalyzed Stereoselective Synthesis of Giycosyl Trichloroacetamides and Their Conversion to a- and D-Urea Glycosides                                             297

15.1  Introduction, 297

15.2  Development of the Palladium(II)-Catalyzed Glycal Trichloroacetimidate Rearrangement, 300

15.3  Stereoselective Synthesis of Glycosyl Ureas from Glycal Trichloroacetimidates, 307

15.4  Development of the Stereoselective Nickel-Catalyzed Transformation of Glycosyl Trichloroacetimidates to Trichloroacetamides, 310

15.5  Transformation of Glycosyl Trichloroacetimidates into ct- and 13-Urea Glycosides, 317

15.6  Mechanistic Studies on the Nickel-Catalyzed Transformation of Glycosyl Trichloracetimidates, 317

15.7  Conclusions, 323

References, 323

Index