Domino and Intramolecular Rearrangement Reactions as Advanced Synthetic Methods in Glycoscience

The book consists of a brief introduction, a foreward provided by professor Danishefsky of Columbia University, and about 14 - 16 chapters, each written by one or two eminent scholars/authors describing their recent research in the area of either domino reactions or intramolecular rearrangements in carbohydrate chemistry. Three or four chapters will be reviews. The domino (cascade, tandem) reactions are always intramolecular. They are usually very fast, clean and offer highly complex structures in a one pot process. Intramolecular rearrangements offer very similar advantages and often lead to highly complex products as well. Although many recently isolated carbohydrates fulfill various sophisticated functions, their structures are often very complex. The editors cover the broadest scope of novel methodologies possible. All the synthetic and application aspects of domino/cascade reactions are explored in this book. A second theme that will be covered is intramolecular rearrangement, which is also fast, stereoselective, and often constitutes one or more steps of domino / cascade process. Selected examples of intramolecular rearrangements are presented. Together, both processes offer an elegant and convenient approach to the synthesis of many complex molecules, which are normally difficult to synthesize via alternative routes. It appears that domino and intramolecular rearrangements are ideally suited to synthesize certain specific modified monosaccharides. What is particularly important is that both processes are intermolecular and almost always yield products with very well-defined stereochemistry. This high definition is absolutely crucial when synthesizing advanced, modified mono and oligosaccharides. The choice of contributors reflects an emphasis on both therapeutic and pharmacological aspects of carbohydrate chemistry.

Auteur

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.

Contenu
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 BernetVasella 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 PyranoFurano 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 Reac...