Organic Azides Syntheses and Applications

by Brä; se, Stefan; Banert, Klaus

• ISBN13: 9780470519981
• ISBN10: 0470519983
• Edition: 1st
• Format: Hardcover
• Copyright: 2010-02-01
• Publisher: Wiley

Summary

Most current state-of-the-art overview of this important class of compounds, encompassing many new and emerging applications The number of articles on organic azides continues to increase tremendously; on average, there are more than 1000 new publications a year Covers basic chemistry as well as state-of-the-art applications in life science and materials science World-ranked authors describe their own research in the wider context of azide chemistry Includes a chapter on safe synthesis and handling (azides can decompose explosively)

Author Biography

Stefan Bräse was born in Kiel, Germany, in 1967 and studied chemistry in Göttingen, Bangor (UK) and Marseille (France). In 1995, he obtained his doctorate after working with Armin de Meijere at the University of Göttingen. After post-doctoral appointments at Uppsala University, Sweden (J.-E. Bäckvall) and The Scripps Research Institute, La Jolla, USA (K. C. Nicolaou), he began his independent research career at the RWTH Aachen associated with Dieter Enders in1997 and finished his habilitation in 2001. He became Professor at the University of Bonn that same year. Since 2003, he is Full Professor at the University of Karlsruhe  - in October 2009 renamed to the Karlsruhe Institute of Technology. Stefan Bräse has published more than 100 publications and is recipient of the ORCHEM award in 2000. His research interests include methods in drug-discovery (including drug delivery), combinatorial chemistry towards the synthesis of biologically active compounds, total synthesis of natural products and nanotechnology.

Table of Contents

Foreword

Preface

List of Contributors

Abbreviations

Synthesis + Safety

Safety Issues about Azide Compounds

Introduction

Properties that impose restrictions on lab-scale handling of azides

Laboratory safety instructions for the small scale synthesis of azido compounds

Analyzing safety-related properties of azides

References

Large Scale Preparation of Azides

Introduction

Precursor azides, technical production and properties

Examples for the use of azides on a technical scale

The future of commercial-scale azide chemistry

References

Synthesis of Azides

Introduction

Synthesis of Alkyl Azides

Synthesis of Aryl Azides

Synthesis of Acyl Azides

References

Azides by Hydroazidination Reactions

Introduction

Conjugate Addition of Hydrazoic Acid and Its Derivatives

Addition of Hydrazoic Acid and its Derivatives to Non-Activated Olefins

Cobalt-Catalyzed Hydroazidation

Conclusion

References

Reactions

The Chemistry of Vinyl, Allenyl, and Ethynyl Azides

Introduction and Early Synthetic Methods for Vinyl Azides

Routes to Vinyl Azides Developed in the Period 1965 - 1970

New Methods to Prepare Vinyl Azides

Reactions of Vinyl Azides

The Chemistry of Allenyl Azides

Generation of Ethynyl Azides

Conclusion

References

Small Rings by Azide Chemistry

Introduction

2H-Azirines

Aziridines

Triaziridines

Azetidinones

References

Schmidt Rearrangement Reactions with Alkyl Azides

Introduction and Early Attempts (1940-1960)

Schmidt reactions of alkyl azides with carbonyl compounds

Schmidt reactions of alkyl azides with carbocations

Metal-mediated Schmidt reactions of alkyl azides with alkenes and alkynes

Reactions of alkyl azides with a,b-unsaturated ketones

Reactions of alkyl azides with epoxides

Combined Schmidt rearrangement cascade reactions

Schmidt rearrangements in the total synthesis of natural products

Schmidt rearrangements of alkyl azides in the synthesis of interesting non-natural products

Schmidt rearrangements of hydroxyalkyl azides toward biologically relevant compounds

Final Comments

Acknowledgments

References

Radical Chemistry with Azides

Introduction

Addition of the azidyl radical onto alkenes

Azidation of carbon centered radicals

Aminyl and amidyl radicals via reduction of azides

Fragmentation reaction of -azidoalkyl radicals

Conclusions

Cycloaddition Reactions with Azides

Huisgen 1,3-dipolar cycloaddition

Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC)

Acceleration of the Click Reaction

Copper-free Click chemistry

Ruthenium-Catalyzed Azide-Alkyne Cycloaddition (RuAAC)

Use of other metals for the cycloaddition of azides and alkynes: Ni(II), Pt(II), Pd(II)

Cycloaddition reactions with azides for the synthesis of tetrazoles

Click chemistry for the synthesis of dihydrotriazoles

Cycloaddition reactions with azides to give thiatriazoles

References

Dipolar Cycloaddition Reactions in Peptide Chemistry

Introduction

Amino Acid Derivatives by DCR

Peptide Backbone Modifications by DCR

Other Peptide Modifications by DCR

Macrocyclization by DCR

Dendrimers and Polymers

Isotopic Labeling by DCR

Perspective

References

Photochemistry of Azides: The Azide/Nitrene Interface

Introduction

Photochemistry of hydrazoic acid (HN₃)

Photochemistry of alkyl azides

Photochemistry of vinyl azides

Photochemistry of carbonyl azides and azide esters

Photochemistry of phenyl azide and its simple derivatives

Conclusion

Acknowledgements

References

Organoazides and Transition Metals

Introduction

Metal complexes co-crystallized with an organoazide

Cationic metal complexes with organoazide containing anions

Metal complexes with ligands bearing a non-coordinating organoazide unit

Metal complexes with an intact, coordinating and linear organoazide ligand

Metal complexes with an intact, coordinating but bent organoazide ligand

Organoazides reacting with other metal bound ligands

References

Material Sciences

Azide-Containing High Energy Materials

Introduction

Organic Azides

Acknowledgments

References

Azide Chemistry for Molecular Machines

Introduction

Purely organic rotaxanes and catenanes

Transition metal templated approaches

Conclusion

References

Application in Bioorganic Chemistry

Aza-Wittig Reaction in Natural Product Syntheses

Introduction

Intermolecular aza-Wittig reaction

Intramolecular aza-Wittig reaction

Conclusions

Acknowledgments

References

Azides in Carbohydrate Chemistry

Introduction

Synthesis of Azide-Containing Carbohydrates

Azides as Protecting Groups during Aminoglycoside Synthesis

Azides as Non-Participating Neighboring Groups in Glycosylations

Glycosyl Azides as Precursors for Glycosyl Amides

Synthesis of Glycoconjugates via Azide-Alkyne [3+2] Cycloaddition

Metabolic Oligosaccharide Engineering

References

Key Word Index

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