Domino and intramolecular rearrangement reactions as advanced synthetic methods in glycoscience / edited by Zbigniew J. Witczak, Roman Bielski.

Format:

Book

Contributor:

Witczak, Zbigniew J., 1947- editor.

Bielski, Roman, 1946- editor.

Series:

THEi Wiley ebooks.

Language:

English

Subjects (All):

Glycosides--Physiological effect.

Glycosides.

Glycosides--Analysis.

Physical Description:

1 online resource (374 pages)

Edition:

1st ed.

Place of Publication:

Hoboken, New Jersey : Wiley, 2016.

System Details:

Access using campus network via VPN at home (THEi Users Only).

Summary:

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.

Contents:

Intro

Domino and Intramolecular Rearrangement Reactions as Advanced Synthetic Methods in Glycoscience

Contents

Foreword

Preface

Acknowledgments

List of Contributors

Abbreviations

1 Introduction to Asymmetric Domino Reactions

1.1 Introduction

1.2 Asymmetric Domino Reactions using Chiral Carbohydrate Derivatives

1.2.1 Stereocontrolled Domino Reactions of Chiral Carbohydrate Derivatives

1.2.2 Enantioselective Domino Reactions Catalyzed by Chiral Carbohydrate Derivatives

1.3 Conclusions

References

2 Organocatalyzed Cascade Reaction in Carbohydrate Chemistry

2.1 Introduction

2.2 C-Glycosides

2.3 Amine-Catalyzed Knoevenagel-Additions

2.4 Multicomponent Reactions

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

2.6 Conclusions

3 Reductive Ring-Opening in Domino Reactions of Carbohydrates

3.1 Introduction

3.2 Bernet-Vasella Reaction

3.2.1 Domino Reductive Fragmentation/Reductive Amination

3.2.2 Domino Reductive Fragmentation/Barbier-Type Allylation

3.2.3 Domino Reductive Fragmentation/Barbier-Type Propargylation

3.2.4 Domino Reductive Fragmentation/Vinylation

3.2.5 Domino Reductive Fragmentation/Alkylation

3.2.6 Domino Reductive Fragmentation/Olefination

3.2.7 Domino Reductive Fragmentation/Nitromethylation

3.3 Reductive Ring Contraction

3.3.1 Ring Opening/Ketyl-Olefin Annulation

3.3.2 Ring Opening/Intramolecular Carbonyl Alkylation

3.4 Conclusions

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

4.1 Introduction

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

4.3 Exploratory Chemistry for Amino Sugars Domino Reactions

4.4 Domino Reactions Toward Sugar Ring Contraction.

4.4.1 Pyrano-Furano Ring Contraction

4.4.2 Ring Contraction of Furans to Oxetanes

4.5 Macrocyclic Bislactone Synthesis via Domino Reaction

4.6 Sugar Deoxygenation by Domino Reaction

4.7 Conclusions

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

5.1 Introduction

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

5.3 Sulfur-Assisted Multistep Processes and Their use in The De Novo Synthesis of Glycostructures

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

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

5.3.3 Up to Six Steps in One Process: 4'-Substituted Nucleoside Synthesis

5.3.4 Eight Steps in One Process: Beyond Achmatowicz Rearrangement

5.4 Concluding Remarks

5.5 Acknowledgments

6 Thio-Click and Domino Approach to Carbohydrate Heterocycles

6.1 Introduction

6.2 Classification and Reaction Mechanism

6.3 Conclusions

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

7.1 Introduction

7.2 Convertible Isocyanides

7.2.1 CIC Employed in the Ugi Reaction

7.2.2 Resin-Bound CICs

7.2.3 CIC Employed in the Ugi-Smile Reaction

7.2.4 CIC Employed in the Joullié-Ugi Reaction

7.2.5 CIC Employed in the Passerini Reaction

7.2.6 CIC Employed in the Groebke-Blackburn-Bienaymé Reaction

7.2.7 CIC Employed in the Diels-Alder Reaction

7.2.8 Monosaccharide Isocyanides Employed in the Ugi and Passerini Reaction

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

7.3 Conclusions

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

8.1 Introduction

8.2 Spiroketals via a Domino Oxidation/Rearrangement Sequence

8.3 Chromans and Isochromans via Domino Carbopalladation Carbopalladation/Cyclization Sequence

9 Introduction to Rearrangement Reactions in Carbohydrate Chemistry

9.1 Introduction

9.2 Classification

9.3 Chapman Rearrangement

9.4 Hofmann Rearrangement

9.5 Cope Rearrangement

9.6 Ferrier Rearrangement

9.7 Claisen Rearrangement

9.8 Overman Rearrangement

9.9 Baeyer-Villiger Rearrangement

9.10 Ring Contraction

9.11 Conclusions

10 Rearrangement of a Carbohydrate Backbone Discovered "EN ROUTE" to Higher-Carbon Sugars

10.1 Introduction

10.2 Rearrangements Without Changing the Sugar Skeleton

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

10.4 Rearrangements Changing the Structure of a Sugar Skeleton

10.5 Rearrangement of the Sugar Skeleton Discovered EN ROUTE to Higher-Carbon Sugars

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

10.5.2 The Acetylene/Vinyltin Methodology in the Synthesis of HCS

10.5.3 The Allyltin Methodology in the Synthesis of HCS

10.5.4 Rearrangement of the Structure of HCS

10.5.5 Synthesis of Polyhydroxylated Carbocyclic Derivatives with Large Rings

10.6 Conclusions

11 Novel Levoglucosenone Derivatives

11.1 INTRODUCTION

11.2 ADDITIONS TO THE DOUBLE BOND OF THE ENONE SYSTEM LEADING TO THE FORMATION OF NEW RINGS

11.3 REDUCTIONS OF THE CARBONYL GROUP FOLLOWED BY VARIOUS REACTIONS OF THE FORMED ALCOHOL

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

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

11.6 ENZYMATIC REACTIONS OF LEVOGLUCOSENONE.

11.7 High-Tonnage Products from Levoglucosenone

11.7.1 Overman and Allylic Xanthate Rearrangement

11.8 CONCLUSIONS

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

12.1 Introduction

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

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

12.4 Preparation of 6-O-Tosyl-d-Galactal and Reduction with Lithium Aluminum Hydride

12.5 Conclusions

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

13.1 Introduction

13.2 Synthesis of Septanosides

13.2.1 Synthesis of Septanosides via Hemiacetal Formation

13.2.2 Knoevenagel Condensation

13.2.3 Baeyer-Villiger Oxidation of Cyclohexanone Derivatives

13.2.4 Electrophile-Induced Cyclization

13.2.5 Metal-Catalyzed Cyclization

13.2.6 Nicolas-Ferrier Rearrangements

13.2.7 Ring Opening of Carbohydrate-Derived Cyclopropanes

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

13.2.9 Ring Opening of Oxyglycal Derived 1,2-Cyclopropane

13.2.10 Functionalization of Oxepines

13.3 Structure and Conformation of Septanosides

13.3.1 Solid-State Structures and Conformations

13.3.2 Solution-Phase Conformations

13.4 Conclusions

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

14.1 Introduction

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

14.3 Peptide-Scaffold Hybrids

14.4 Sequential Reactions for the Synthesis of Polyannular Heterocycles

14.5 The First Total Synthesis of Amphorogynine C

References.

15 Palladium- and Nickel- Catalyzed Stereoselective Synthesis of Glycosyl Trichloroacetamides and Their Conversion to - and -Urea Glycosides

15.1 Introduction

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

15.3 Stereoselective Synthesis of Glycosyl Ureas from Glycal Trichloroacetimidates

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

15.5 Transformation of Glycosyl Trichloroacetimidates into a- and b-Urea Glycosides

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

15.7 Conclusions

Index

Supplemental Images

EULA.

Notes:

Description based upon print version of record.

Includes bibliographical references and index.

Description based on print version record.

ISBN:

9781119044390

1119044391

9781119044239

1119044235

OCLC:

925426608