Domino and Intramolecular Rearrangement Reactions as Advanced Synthetic Methods in Glycoscience

Zbigniew J. Witczak obtained his Ph.D. from Medical University of Lodz, Faculty of Pharmacy (Poland). After postdoctoral work at Purdue University, he worked in industry (A. E.Staley), then joined the faculty of the School of Pharmacy at University of Connecticut. He moved to Wilkes University, Nesbitt School of Pharmacy in 2000, where he is Full Professor. He has published over ninety research papers and holds six patents in the fields of carbohydrate medicinal and biological chemistry. In 2000 he was awarded the Melville L. Wolfrom Award of the ACS Division of Carbohydrate Chemistry. His research interests are in the area of carbohydrate Synthons including Levoglucosenone and L-Arabinose as template for carbohydrate based therapeutics. Roman Bielski obtained his Ph.D. at the Institute of Organic Chemistry, Polish Academy of Sciences. He is currently a Senior Scientist in Value Recovery, Inc., a partner in Cheminnolab, LLC, and adjunct professor at Wilkes University. Recently he (with M. Tencer) developed a method of enantiomers' resolution requiring no use of chiral compounds. His research interests are origin of homochirality, modification of carbohydrates, solutions to environmental issues and sustainability. He published over three dozen papers and co-authored 18 patents.

Foreword xiii

Preface xv

Acknowledgments xix

List of Contributors xxi

Abbreviations xxv

1 Introduction to Asymmetric Domino Reactions 1
Hélène Pellissier

1.1 Introduction, 1

1.2 Asymmetric Domino Reactions using Chiral Carbohydrate Derivatives, 3

1.2.1 Stereocontrolled Domino Reactions of Chiral Carbohydrate Derivatives, 3

1.2.2 Enantioselective Domino Reactions Catalyzed by Chiral Carbohydrate Derivatives, 8

1.3 Conclusions, 12

References, 13

2 Organocatalyzed Cascade Reaction in Carbohydrate Chemistry 16
Benjamin Voigt and Rainer Mahrwald

2.1 Introduction, 16

2.2 C-Glycosides, 17

2.3 Amine-Catalyzed Knoevenagel-Additions, 20

2.4 Multicomponent 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
Raquel G. Soengas, Sara M. Tomé, and Artur M. S. Silva

3.1 Introduction, 49

3.2 Bernet–Vasella Reaction, 50

3.2.1 Domino Reductive Fragmentation/Reductive Amination, 51

3.2.2 Domino Reductive Fragmentation/Barbier-Type Allylation, 52

3.2.3 Domino Reductive Fragmentation/Barbier-Type Propargylation, 57

3.2.4 Domino Reductive Fragmentation/Vinylation, 59

3.2.5 Domino Reductive Fragmentation/Alkylation, 60

3.2.6 Domino Reductive Fragmentation/Olefination, 61

3.2.7 Domino Reductive Fragmentation/Nitromethylation, 62

3.3 Reductive Ring Contraction, 64

3.3.1 Ring Opening/Ketyl-Olefin Annulation, 65

3.3.2 Ring Opening/Intramolecular Carbonyl Alkylation, 69

3.4 Conclusions, 73

References, 73

4 Domino Reactions Toward Carbohydrate Frameworks for Applications Across Biology and Medicine 76
Vasco Cachatra and Amélia P. Rauter

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

4.4.1 Pyrano–Furano Ring Contraction, 84

4.4.2 Ring Contraction of Furans to Oxetanes, 87

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 Chiral Building Blocks: New Avenues in Glycochemistry 97
Daniele D’Alonzo, Giovanni Palumbo, and Annalisa Guaragna

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

5.3.1 Three Steps in One Process: Double Approach to 4-Deoxy l-(and d-)-Hexoses, 101

5.3.2 Five Steps in One Process: The Domino Way to l-Hexoses (and Their Derivatives), 102

5.3.3 Up to Six Steps in One Process: 4′-Substituted Nucleoside Synthesis, 105

5.3.4 Eight Steps in One Process: Beyond Achmatowicz Rearrangement, 109

5.4 Concluding Remarks, 111

5.5 Acknowledgments, 111

References, 111

6 Thio-Click and Domino Approach to Carbohydrate Heterocycles 114
Zbigniew J. Witczak and Roman Bielski

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
Soumava Santra, Tonja Andreana, Jean-Paul Bourgault, and Peter R. Andreana

7.1 Introduction, 121

7.2 Convertible Isocyanides, 125

7.2.1 CIC Employed in the Ugi Reaction, 125

7.2.2 Resin-Bound CICs, 167

7.2.3 CIC Employed in the Ugi–Smile Reaction, 172

7.2.4 CIC Employed in the Joulli´e–Ugi Reaction, 172

7.2.5 CIC Employed in the Passerini Reaction, 175

7.2.6 CIC Employed in the Groebke–Blackburn–Bienaym´e Reaction, 178

7.2.7 CIC Employed in the Diels–Alder Reaction, 182

7.2.8 Monosaccharide Isocyanides Employed in the Ugi and Passerini Reaction, 183

7.2.9 Methyl isocyanide in the Preparation of the Hydroxy DKP Thaxtomin A, 186

7.3 Conclusions, 187

References, 187

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

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 209
Zbigniew J. Witczak and Roman Bielski

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
S³awomir Jarosz, Anna Osuch-Kwiatkowska, Agnieszka Gajewska, and Maciej Cieplak

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

10.5.1 Synthesis of Higher-Carbon Sugars by the Wittig-Type Methodology, 226

10.5.2 The Acetylene/Vinyltin Methodology in the Synthesis of HCS, 227

10.5.3 The Allyltin Methodology in the Synthesis of HCS, 227

10.5.4 Rearrangement of the Structure of HCS, 230

10.5.5 Synthesis of Polyhydroxylated Carbocyclic Derivatives with Large Rings, 235

10.6 Conclusions, 237

Acknowledgments, 237

References, 237

11 Novel Levoglucosenone Derivatives 240
Roman Bielski and Zbigniew J. Witczak

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

11.7.1 Overman and Allylic Xanthate Rearrangement, 245

11.8 Conclusions, 246

References, 247

12 The Preparation and Reactions of 3,6-Anhydro-d-Glycals 248
Vikram Basava, Emi Hanawa, and Cecilia H. Marzabadi

12.1 Introduction, 248

12.2 Preparation of 3,6-Anhydro-d-Glucal Under Reductive Conditions, 250

12.3 Addition Reactions of 3,6-Anhydro-d-Glucal, 251

12.4 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
Supriya Dey, N. Vijaya Ganesh, and N. Jayaraman

13.1 Introduction, 256

13.2 Synthesis of Septanosides, 258

13.2.1 Synthesis of Septanosides via Hemiacetal Formation, 258

13.2.2 Knoevenagel Condensation, 260

13.2.3 Baeyer–Villiger Oxidation of Cyclohexanone Derivatives, 260

13.2.4 Electrophile-Induced Cyclization, 260

13.2.5 Metal-Catalyzed Cyclization, 261

13.2.6 Nicolas–Ferrier Rearrangements, 262

13.2.7 Ring Opening of Carbohydrate-Derived Cyclopropanes, 263

13.2.8 Ring Opening of Glycal-Derived 1,2-Cyclopropane, 263

13.2.9 Ring Opening of Oxyglycal Derived 1,2-Cyclopropane, 265

13.2.10 Functionalization of Oxepines, 268

13.3 Structure and Conformation of Septanosides, 269

13.3.1 Solid-State Structures and Conformations, 270

13.3.2 Solution-Phase Conformations, 273

13.4 Conclusions, 275

Acknowledgments, 276

References, 276

14 Rearrangements in Carbohydrate Templates to theWay to Peptide-Scaffold Hybrids and Functionalized Heterocycles 279
Bernardo Herrad´on, Irene de Miguel, and Enrique Mann

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 Glycosyl Trichloroacetamides and Their Conversion to 𝛂- and 𝛃-Urea Glycosides 297
Nathaniel H. Park, Eric T. Sletten, Matthew J. McKay, and Hien M. Nguyen

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 α- and β-Urea Glycosides, 317

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

15.7 Conclusions, 323

References, 323

Index 325