Isonitrile Chemistry

1st Edition - January 28, 1971
Editor: Ivar Ugi
Language: English
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 1 5 7 3 3 - 9

Organic Chemistry, Volume 20: Isonitrile Chemistry discusses the fundamental aspects of the chemistry of isonitriles. This book provides an introduction to as well as a thorough… Read more

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Organic Chemistry, Volume 20: Isonitrile Chemistry discusses the fundamental aspects of the chemistry of isonitriles. This book provides an introduction to as well as a thorough coverage of isonitrile chemistry. Organized into 10 chapters, this volume begins with an overview of the general properties and structure of isonitriles. This text then examines the quantitative study of the kinetics of isonitrile rearrangement as well as the principal resonance structure of the isonitrile molecule. Other chapters consider the experimental and theoretical findings on the fall-off behavior of the unimolecular rate constants of different isonitriles with pressure. This book discusses as well the behavior of isonitriles toward a center of low electron density, which is particularly manifested in the reactivity of alkyl and aryl isonitriles toward diborane and alkyl or arylboranes. The final chapter deals with the inorganic coordination chemistry of isonitriles. This book is a valuable resource for organic chemists.

List of Contributors

Preface

1. The Structure of Isonitriles

I. The History of the Structure of Isonitriles

II. Some Physicochemical Consequences of the Structure of the Isocyano Group

References

2. Isonitrile Syntheses

I. Introduction

II. The Dehydration of N-Monosubstituted Formamides and Related α-Eliminations

III. The Classical Isonitrile Syntheses and Related Reactions

IV. Miscellaneous Reactions by Which Isonitriles Are Formed

References

3. Kinetics of the Isonitrile-Nitrile Rearrangement

I. Introduction

II. Thermal Rearrangement

III. External Excitation

References

4. Simple α-Additions

I. Introduction

II. α-Addition Reactions of Isonitriles with Reactive Hydrogen Compounds

III. α-Addition Reactions of Isonitriles with Reactive Halogen Compounds

IV. Oxidation of Isonitriles

V. Reduction of Isonitriles

VI. Reactions with Carbenes and Nitrenes

VII. Reaction with Organometallic Compounds

VIII. Radical Reactions of Isonitriles

IX. Reactions Related to α-Additions

References

5. Cyclization Reactions

I. Introduction

II. Four-Membered Rings

III. Five-Membered Rings

IV. Six-Membered Rings

V. Seven-Membered Rings

References

6. The Reaction of Isonitriles with Boranes

I. Isonitrile-Organoborane Reactions

II. Isonitrile-Organoaluminum and Cyanide-Organoaluminum Reactions

III. Cyanide-Organoborane Reactions

IV. Related Reactions: The Reaction of Carbon Monoxide and Other Lewis Bases with Organoboranes

References

7. The Passerini Reaction and Related Reactions

I. Introduction

II. α-Acyloxycarbonamides

III. The Mechanism of the Passerini Reaction

IV. Tetrazoles

V. α-Hydroxyamides

VI. α,γ-Diketoamides

References

8. Four-Component Condensations and Related Reactions

I. Introduction and General Remarks

II. Hydantoin-4-imides and 2-Thiohydantoin-4-imides

III. Acylated α-Amino- and α-Hydrazinocarbonamides

IV. Stereoselective Syntheses and the Reaction Mechanism of 4 C C

V. β-Lactams and Penicillanic Acid Derivatives

VI. Urethanes

VII. The Bucherer-Bergs Reaction

VIII. N-Alkyl-3-acyl-4-hydroquinoline-4-carbonamides

IX. Diacylimides, Amides, Thioamides, Selenoamides, and Amidines of α-Amino Acids

X. Tetrazoles

References

9. Peptide Syntheses

I. The General Concept

II. The Present Status of Classical Methods

III. Potential Advantages of the 4 C C Concept

IV. Isonitrile and Amine Components—Model Reactions

V. Tactics of the 4 C C Peptide Synthesis

References

10. Coordinated Isonitriles

I. Introduction

II. Structure and Bonding in Isonitrile Complexes

III. Reactions of Coordinated Isonitriles

IV. The Synthesis of Metal Isonitrile Complexes

References

Addendum Recent Developments in Isonitrile Chemistry

Author Index

Subject Index