Polymers as Aids in Organic Chemistry

Polymers as Aids in Organic Chemistry covers the broad classifications and application of polymers in organic chemistry. This book is organized into 15 chapters that focus on the transformation of polymers and their role in other reagents that must be easily separated from their final product. After a brief introduction to polymer chemistry, the book presents a tabulation of the various types of polymers that have been used and the methods for their characterization. It then discusses the use of polymers as supports in peptide, oligonucleotide, and oligosaccharide chemistry; in peptide sequencing; in monofunctionalized difunctional compounds preparation, as aids in asymmetric syntheses; and as trapping agents in the determination of reaction intermediates. The subsequent chapters describe the use of polymers as catalysts, with particular emphasis on transition metals immobilized in the polymer matrix and used as catalysts. The concluding chapters examine polymer-immobilized compounds, enzymes, and whole cells that have been used to carry out a large number of reaction, most of which impinge on the area of organic chemistry. Polymer scientists and researchers and organic chemists will find this book invaluable.

Preface

1. Introduction

I. History

II. Development of Polymer Science and Technology

III. Definition and Classification of Polymers

IV. Preparation of Synthetic Polymers

V. Properties of Polymers

VI. Synthesis of Functionalized Polymers

VII. Types of Functionalized Polymers

VIII. General Chemical Reactions of Polymers

IX. Polymers as Aids in Organic Synthesis

X. Kinetics of Polymer-Analogous Reactions

XI. Literature on Solid-Phase Synthesis

References

2. Polymeric Support Materials

I. Introduction

II. Styrene-Based Polymers

III. Functionalization of Styrene-Based Polymers via Chloromethylation and Other Methods

IV. Miscellaneous Polymer Supports

References

3• Determination of Functionalization in Polymer Supports

I. Introduction

II. Chemical Methods for Functional Group Analysis of Polymers

III. Physical and Physicochemical Methods of Determining Functional Groups in Polymers

IV. Physical and Chemical Nature of Immobilization of Reactive Sites on Polymers

V. Use of Radiolabeled Reagents to Follow the Changes in Resin Functionalities

VI. Reporting of Results

References

4. Polypeptide Synthesis on Polymer Supports

I. Introduction and History

II. Basic Principles of Merrifield's Solid-Phase Peptide Synthesis

III. Supports for Solid-Phase Peptide Synthesis

IV. Linkage of the First Amino Acid to the Polymer

V. Protecting Groups Used in Solid-Phase Peptide Synthesis

VI. Coupling of Successive Amino Acids to Resin-Bound Amino Acids

VII. Cleavage of the Resin-Peptide Bond

VIII. Monitoring of Solid-Phase Peptide Synthesis

IX. Automation in Solid-Phase Peptide Synthesis

X. Racemization Problems in Solid-Phase Peptide Products

XI. Purification of Solid-Phase Peptide Products

XII. Problems in Solid-Phase Synthesis

XIII. Solid-Phase Coupling of N-Carboxylanhydrides (NCA)

XIV. Solid-Phase Synthesis Using Side-Chain Functionalities for Attachment to Polymers and Bidirectional Extension of Peptide Chains

XV. Fragment Condensation Strategy in Solid-Phase Peptide Synthesis

References

5. Oligonucleotide Synthesis on Polymer Supports

I. Introduction

II. General Principles of Solid-Phase Oligonucleotide Synthesis

III. Polymer Supports

IV. Functionalization of Polymer Supports

V. Strategies Used for Oligonucleotide Synthesis on Polymer Supports

VI. Protection of Reactive Groups

VII. Cleavage of the Protecting Groups

VIII. Attachment of the Polymeric Carrier to the Nucleotide or Nucleoside

IX. Elongation of the Nucleotide Chain on the Polymer Support

X. Cleavage of the Polymer-Nucleoside/Nucleotide Bond

XI. Monitoring in Polymer-Supported Oligonucleotide Synthesis

XII. Purification of Synthetic Oligonucleotides

XIII. Synthesis of Oligoribonucleotides on Polymer Supports

XIV. Miscellaneous Application of Polymers in Polynucleotide Synthesis

XV. Advantages and Limitations

References

6. Oligosaccharide Synthesis on Polymer Supports

I. Introduction

II. Basic Principles of Polymer-Supported Oligosaccharide Synthesis

III. Polymer Supports for the Synthesis of Oligosaccharides

IV. Linkage of the First Sugar Molecule to the Polymer Support and Product Removal

V. Protecting Groups in Oligosaccharide Synthesis Employing Polymer Supports

VI. Mechanism and Steric Control in Successive Coupling of Monosaccharide Residues on a Polymer Support

VII. Miscellaneous Applications of Polymers in the Carbohydrate Field

VIII. Monitoring of Solid-Phase Oligosaccharide Synthesis

IX. Advantages, Limitations, and Future Scope of the Use of Polymer Supports in Polysaccharide Synthesis

References

7. Peptide Synthesis Using Polymeric Active Esters

I. Introduction

II. Principles of Peptide Synthesis Using Polymeric Active Esters

III. Polymeric Active Esters Used for Peptide Synthesis

IV. Synthesis of Cyclic Peptides Using Polymeric Active Esters

V. Scope and Limitations of the Polymeric Active Ester Method for Peptide Synthesis

References

8. Solid-Phase Sequencing of Peptides and Proteins

I. Introduction

II. Solid-Phase Edman Degradation Using Polymeric Reagents

III. Solid-Phase Degradation Employing Polymer-Bound Peptides

IV. Other Polymer Supports for Solid-Phase Sequencing

V. Attachment of the Peptide to the Polymer Support

VI. Automation in Solid-Phase Sequencing

VII. Solid-Phase Sequencing of Peptides from the Carboxyl Terminus

VIII. Scope and Limitations of Solid-Phase Sequencing Methods

References

9. Polymeric Supports in General Organic Chemistry

I. Introduction

II. Alkylation and Acylation of Esters Using Functionalized Carriers

III. Dieckmann Cyclization of Polymer-Bound Esters

IV. Cyclization of Large Ring Compounds on Polymeric Supports

V. Monofunctionalization of Polymer-Bound Compounds

VI. Synthesis of Threaded Macrocyclic Systems (Hooplanes)

VII. Photochemical Applications

References

10. Polymer-Supported Asymmetric Synthesis and Resolution of Racemates Using Asymmetric Polymeric Materials

I. Introduction

II. Asymmetric Syntheses of Polymeric Supports

III. Resolution of Racemates Using Polymeric Materials

References

11. Application of Polymeric Supports in Identifying Reaction Intermediates

I. Introduction

II. General Strategy Used for Trapping Reaction Intermediates Employing Polymeric Supports

References

12. Polymer-Bound Reagents

I. Introduction

II. Polymeric Oxidizing Reagents

III. Polymeric Oxidation-Reduction Reagents

IV. Polymeric Reducing Reagents

V. Polymeric Group Transfer Reagents

VI. Polymeric Coupling Agents

VII. Miscellaneous Reagents

References

13. Polymer-Bound Catalysts (I)

I. Introduction

II. Ion-Exchange Resins as General Acid-Base Catalysts

III. Polystyrene-Aluminum Chloride as a Lewis Acid Catalyst

IV. Polymer-Based "Super Acid" Catalysts

V. Polymeric Esterolytic Catalysts

VI. Polymer-Supported Phase-Transfer Catalysts

VII. Polymeric Triphase Catalysts

VIII. Polymer-Based Photosensitizers

References

14. Polymer-Bound Catalysts (II) Transition Metal Complexes Bound to Polymers

I. Polymer-Supported Transition Metal Catalysts

II. Principles of Homogeneous Transition Metal Complex Catalysts

III. Preparation of Polymer-Bound Transition Metal Complexes

IV. Structure of Polymeric Catalysts

V. Types of Reactions Catalyzed by Polymer-Anchored Catalysts

VI. Asymmetric Organic Synthesis via Transition Metal Catalysts Bound to Polymeric Chiral Ligands

References

15. Polymers as Aids in Related Areas of Chemistry

I. Introduction

II. Applications in Analytical Chemistry

III. Polymer-Bound Agriculturally and Pharmacologically Active Agents

IV. Applications in Biochemistry

References

Index