Reactions of Organosulfur Compounds

Organic Chemistry, Volume 37: Reactions of Organosulfur Compounds covers the basics of organosulfur chemistry and the characteristics of organically bound sulfur, with an emphasis on reactions, particularly those of synthetic utility. The book discusses the preparation, nature, stereochemical aspects, reactions, and the kinetic and thermodynamic assessment of the stability of sulfur-containing carbanions; the preparation and reactions of sulfur ylides; and the preparation, assessment of stability, and reactions of sulfur-containing carbocations. The text also describes preparation, assessment of stability, nature, and reactions of sulfur-containing radicals, organosulfur carbenes, and carbenoids; as well as the the pericyclic reactions of organosulfur compounds. Chemists, biochemists, and students taking related courses will find the book useful.

List of Tables

Preface

Acknowledgments

Abbreviations

1 Introduction

1.1 Prologue

1.2 A Word on Odor

1.3 Sulfur in the Natural Environment

1.4 Nomenclature and Synthesis of Organosulfur Compounds

1.5 3d Orbital Effects

1.6 Other Bonding Properties of Sulfur

1.7 Spectroscopic Properties of Sulfur

1.8 Penicillin and Cephalosporin Chemistry: A Microcosm of Organosulfur Chemistry

References

2 Sulfur-Containing Carbanions

2.1 Introduction

2.2 Preparation

2.3 Kinetic and Thermodynamic Assessment of Stability of Sulfur-Containing Carbanions

2.4 The Nature of Carbanion Stabilization by Sulfur

2.5 Stereochemical Aspects of α-Sulfonyl Carbanions

2.6 Stereochemical Aspects of α-Sulfìnyl Carbanions

2.7 Reactions of Sulfur-Containing Carbanions

References

3 Sulfur Ylides

3.1 Preparation

3.2 σ- and π-Sulfuranes

3.3 Thiabenzenes 96

3.4 Thiocarbonyl Ylides (Thione Ylides)

3.5 Reactions of Sulfur Ylides

References

4 Sulfur-Containing Carbocations

4.1 Introduction

4.2 Generation of Sulfur-Containing Carbocations

4.3 Assessment of Stability of Sulfur-Containing Carbocations

4.4 Neighboring Group Participation by Divalent Sulfur

4.5 Reactions of Thiocarbocations

4.6 The Pummerer Rearrangement

4.7 Beckmann Fragmentation of α-Alkylthioketoximes

4.8 Carbocations Containing the Sulfinyl and Sulfonyl Groups

4.9 Carbocations Containing the Disulfide Group

References

5 Sulfur-Containing Radicals

5.1 Introduction

5.2 Generation and Reactions of Sulfur-Containing Radicals

5.3 Kinetic Assessment of Stability of Sulfur-Substituted Radicals

5.4 The Study of Sulfur-Containing Radicals by Electron Spin Resonance Spectroscopy

5.5 The Nature of Radical Stabilization by Sulfur

5.6 α-Disulfìde Radicals

5.7 α-Sulfìnyl Radicals

5.8 α-Sulfonyl Radicals

5.9 The Dibenzenesulfenamidyl Radical

5.10 The Stevens Rearrangement

5.11 The Wittig Rearrangement

5.12 Sulfur-Centered Radicals

References

6 Organosulfur Carbenes and Carbenoids

6.1 Introduction

6.2 Generation

6.3 Reactions of α-Thiomethylenes: Cycloaddition to Multiple Bonds

6.4 Other Reactions of α-Thiomethylenes: General Survey

6.5 Reactions of ß-, γ-, and δ-Thiomethylenes

6.6 Sulfinyl- and Sulfonylmethylenes

References

7 Pericyclic Reactions of Organosulfur Compounds

7.1 Introduction

7.2 Sigmatropic Rearrangements

7.3 Electrocyclic Processes

7.4 Cycloaddition Reactions

7.5 Cycloelimination Reactions

References

Appendix A Bibliography of Recent Books on Sulfur

Appendix B Additional Tables

Index