Organic Azides
Syntheses and Applications
1. Edition December 2009
536 Pages, Hardcover
Wiley & Sons Ltd
ISBN:
978-0-470-51998-1
John Wiley & Sons
Short Description
In the past decade, completely new perspectives have been developed for the use of azides in peptide chemistry, combinatorial chemistry, and heterocyclic synthesis. The world-ranked authors of Organic Azides describe their own research in the wider context of azide chemistry and include a vital chapter on safe synthesis and handling. This first state-of-the-art overview of this important class of compounds will be of vital interest to organic chemists, drug discovery researchers, materials scientists and those interested in the chemistry of natural products.
* 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)
Foreword: Rolf Huisgen and Barry Sharpless
Preface
List of Contributors
Abbreviations
PART 1: SYNTHESIS + SAFETY
Chapter 1: Safety Issues about Azide Compounds
Thomas Keicher and Stefan Löbbecke
1.1 Introduction
1.2 Properties that impose restrictions on lab-scale handling of azides
1.3 Laboratory safety instructions for the small scale synthesis of azido compounds
1.4 Analyzing safety-related properties of azides
1.5 References
Chapter 2: Large Scale Preparation of Azides
Jürgen Haase
2.1 Introduction
2.2 Precursor azides, technical production and properties
2.3 Examples for the use of azides on a technical scale
2.4 The future of commercial-scale azide chemistry
2.5 References
Chapter 3: Synthesis of Azides
Teresa M. V. D. Pinho e Melo
3.1 Introduction
3.2 Synthesis of Alkyl Azides
3.3 Synthesis of Aryl Azides
3.4 Synthesis of Acyl Azides
3.5 References
Chapter 4: Azides by Hydroazidination Reactions
Jérôme Waser and Erick Carreira
4.1 Introduction
4.2 Conjugate Addition of Hydrazoic Acid and Its Derivatives
4.3 Addition of Hydrazoic Acid and its Derivatives to Non-Activated Olefins
4.4 Cobalt-Catalyzed Hydroazidation
4.5 Conclusion
4.6 References
PART 2: REACTIONS
Chapter 5: The Chemistry of Vinyl, Allenyl, and Ethynyl Azides
Klaus Banert
5.1 Introduction and Early Synthetic Methods for Vinyl Azides
5.2 Routes to Vinyl Azides Developed in the Period 1965 - 1970
5.3 New Methods to Prepare Vinyl Azides
5.4 Reactions of Vinyl Azides
5.5 The Chemistry of Allenyl Azides
5.6 Generation of Ethynyl Azides
5.7 Conclusion
5.8 References
Chapter 6: Small Rings by Azide Chemistry
Thomas Gilchrist and Maria Alves
6.1 Introduction
6.2 2H-Azirines
6.3 Aziridines
6.4 Triaziridines
6.5 Azetidinones
6.6 References
Chapter 7: Schmidt Rearrangement Reactions with Alkyl Azides
Scott Grecian and Jeffrey Aubé
7.1 Introduction and Early Attempts (1940-1960)
7.2 Schmidt reactions of alkyl azides with carbonyl compounds
7.3 Schmidt reactions of alkyl azides with carbocations
7.4 Metal-mediated Schmidt reactions of alkyl azides with alkenes and alkynes
7.5 Reactions of alkyl azides with a,b-unsaturated ketones
7.6 Reactions of alkyl azides with epoxides
7.7 Combined Schmidt rearrangement cascade reactions
7.8 Schmidt rearrangements in the total synthesis of natural products
7.9 Schmidt rearrangements of alkyl azides in the synthesis of interesting non-natural products
7.10 Schmidt rearrangements of hydroxyalkyl azides toward biologically relevant compounds
7.11 Final Comments
7.12 Acknowledgments
7.13 References
Chapter 8: Radical Chemistry with Azides
Ciril Jimeno and Philippe Renaud
8.1 Introduction
8.2 Addition of the azidyl radical onto alkenes
8.3 Azidation of carbon centered radicals
8.4 Aminyl and amidyl radicals via reduction of azides
8.5 Fragmentation reaction of alpha-azidoalkyl radicals
8.6 Conclusions
Chapter 9: Cycloaddition Reactions with Azides
C. Schilling, N. Jung and Stefan Bräse
9.1 Huisgen 1,3-dipolar cycloaddition
9.2 Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC)
9.3 Acceleration of the Click Reaction
9.4 Copper-free Click chemistry
9.5 Ruthenium-Catalyzed Azide-Alkyne Cycloaddition (RuAAC)
9.6 Use of other metals for the cycloaddition of azides and alkynes: Ni(II), Pt(II), Pd(II)
9.7 Cycloaddition reactions with azides for the synthesis of tetrazoles
9.8 Click chemistry for the synthesis of dihydrotriazoles
9.9 Cycloaddition reactions with azides to give thiatriazoles
9.10 References
Chapter 10: Dipolar Cycloaddition Reactions in Peptide Chemistry
Christian Wenzel Tornøe and Morten Meldal
10.1 Introduction
10.2 Amino Acid Derivatives by DCR
10.3 Peptide Backbone Modifications by DCR
10.4 Other Peptide Modifications by DCR
10.5 Macrocyclization by DCR
10.6 Dendrimers and Polymers
10.7 Isotopic Labeling by DCR
10.8 Perspective
10.9 References
Chapter 11: Photochemistry of Azides: The Azide/Nitrene Interface
Matthew Platz and Nina Gritsan
11.1 Introduction
11.2 Photochemistry of hydrazoic acid (HN3)
11.3 Photochemistry of alkyl azides
11.4 Photochemistry of vinyl azides
11.5 Photochemistry of carbonyl azides and azide esters
11.6 Photochemistry of phenyl azide and its simple derivatives
11.7 Conclusion
11.8 Acknowledgements
11.9 References
Chapter 12: Organoazides and Transition Metals
Werner Thiel
12.1 Introduction
12.2 Metal complexes co-crystallized with an organoazide
12.3 Cationic metal complexes with organoazide containing anions
12.4 Metal complexes with ligands bearing a non-coordinating organoazide unit
12.5 Metal complexes with an intact, coordinating and linear organoazide ligand
12.6 Metal complexes with an intact, coordinating but bent organoazide ligand
12.7 Organoazides reacting with other metal bound ligands
12.8 References
PART 3: MATERIAL SCIENCES
Chapter 13: Azide-Containing High Energy Materials
Thomas Klapötke and Burkhard Krumm
13.1 Introduction
13.2 Organic Azides
13.3 Acknowledgments
13.4 References
Chapter 14: Azide Chemistry for Molecular Machines
Stephanie Durot, Julien Fry, Jean-Pierre Sauvage and Christian Took
14.1 Introduction
14.2 Purely organic rotaxanes and catenanes
14.3 Transition metal templated approaches
14.4 Conclusion
14.5 References
PART 4: APPLICATION IN BIOORGANIC CHEMISTRY
Chapter 15: Aza-Wittig Reaction in Natural Product Syntheses
Francisco Palacios, Concepción Alonso, Domitila Aparicio, Gloria Rubiales and Jesús M. de los Santo
15.1 Introduction
15.2 Intermolecular aza-Wittig reaction
15.3 Intramolecular aza-Wittig reaction
15.4 Conclusions
15.5 Acknowledgments
15.6 References
Chapter 16: Azides in Carbohydrate Chemistry
Henning S. G. Beckmann and Valentin Wittmann
16.1 Introduction
16.2 Synthesis of Azide-Containing Carbohydrates
16.3 Azides as Protecting Groups during Aminoglycoside Synthesis
16.4 Azides as Non-Participating Neighboring Groups in Glycosylations
16.5 Glycosyl Azides as Precursors for Glycosyl Amides
16.6 Synthesis of Glycoconjugates via Azide-Alkyne [3+2] Cycloaddition
16.7 Metabolic Oligosaccharide Engineering
16.8 References Key Word Index
Preface
List of Contributors
Abbreviations
PART 1: SYNTHESIS + SAFETY
Chapter 1: Safety Issues about Azide Compounds
Thomas Keicher and Stefan Löbbecke
1.1 Introduction
1.2 Properties that impose restrictions on lab-scale handling of azides
1.3 Laboratory safety instructions for the small scale synthesis of azido compounds
1.4 Analyzing safety-related properties of azides
1.5 References
Chapter 2: Large Scale Preparation of Azides
Jürgen Haase
2.1 Introduction
2.2 Precursor azides, technical production and properties
2.3 Examples for the use of azides on a technical scale
2.4 The future of commercial-scale azide chemistry
2.5 References
Chapter 3: Synthesis of Azides
Teresa M. V. D. Pinho e Melo
3.1 Introduction
3.2 Synthesis of Alkyl Azides
3.3 Synthesis of Aryl Azides
3.4 Synthesis of Acyl Azides
3.5 References
Chapter 4: Azides by Hydroazidination Reactions
Jérôme Waser and Erick Carreira
4.1 Introduction
4.2 Conjugate Addition of Hydrazoic Acid and Its Derivatives
4.3 Addition of Hydrazoic Acid and its Derivatives to Non-Activated Olefins
4.4 Cobalt-Catalyzed Hydroazidation
4.5 Conclusion
4.6 References
PART 2: REACTIONS
Chapter 5: The Chemistry of Vinyl, Allenyl, and Ethynyl Azides
Klaus Banert
5.1 Introduction and Early Synthetic Methods for Vinyl Azides
5.2 Routes to Vinyl Azides Developed in the Period 1965 - 1970
5.3 New Methods to Prepare Vinyl Azides
5.4 Reactions of Vinyl Azides
5.5 The Chemistry of Allenyl Azides
5.6 Generation of Ethynyl Azides
5.7 Conclusion
5.8 References
Chapter 6: Small Rings by Azide Chemistry
Thomas Gilchrist and Maria Alves
6.1 Introduction
6.2 2H-Azirines
6.3 Aziridines
6.4 Triaziridines
6.5 Azetidinones
6.6 References
Chapter 7: Schmidt Rearrangement Reactions with Alkyl Azides
Scott Grecian and Jeffrey Aubé
7.1 Introduction and Early Attempts (1940-1960)
7.2 Schmidt reactions of alkyl azides with carbonyl compounds
7.3 Schmidt reactions of alkyl azides with carbocations
7.4 Metal-mediated Schmidt reactions of alkyl azides with alkenes and alkynes
7.5 Reactions of alkyl azides with a,b-unsaturated ketones
7.6 Reactions of alkyl azides with epoxides
7.7 Combined Schmidt rearrangement cascade reactions
7.8 Schmidt rearrangements in the total synthesis of natural products
7.9 Schmidt rearrangements of alkyl azides in the synthesis of interesting non-natural products
7.10 Schmidt rearrangements of hydroxyalkyl azides toward biologically relevant compounds
7.11 Final Comments
7.12 Acknowledgments
7.13 References
Chapter 8: Radical Chemistry with Azides
Ciril Jimeno and Philippe Renaud
8.1 Introduction
8.2 Addition of the azidyl radical onto alkenes
8.3 Azidation of carbon centered radicals
8.4 Aminyl and amidyl radicals via reduction of azides
8.5 Fragmentation reaction of alpha-azidoalkyl radicals
8.6 Conclusions
Chapter 9: Cycloaddition Reactions with Azides
C. Schilling, N. Jung and Stefan Bräse
9.1 Huisgen 1,3-dipolar cycloaddition
9.2 Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC)
9.3 Acceleration of the Click Reaction
9.4 Copper-free Click chemistry
9.5 Ruthenium-Catalyzed Azide-Alkyne Cycloaddition (RuAAC)
9.6 Use of other metals for the cycloaddition of azides and alkynes: Ni(II), Pt(II), Pd(II)
9.7 Cycloaddition reactions with azides for the synthesis of tetrazoles
9.8 Click chemistry for the synthesis of dihydrotriazoles
9.9 Cycloaddition reactions with azides to give thiatriazoles
9.10 References
Chapter 10: Dipolar Cycloaddition Reactions in Peptide Chemistry
Christian Wenzel Tornøe and Morten Meldal
10.1 Introduction
10.2 Amino Acid Derivatives by DCR
10.3 Peptide Backbone Modifications by DCR
10.4 Other Peptide Modifications by DCR
10.5 Macrocyclization by DCR
10.6 Dendrimers and Polymers
10.7 Isotopic Labeling by DCR
10.8 Perspective
10.9 References
Chapter 11: Photochemistry of Azides: The Azide/Nitrene Interface
Matthew Platz and Nina Gritsan
11.1 Introduction
11.2 Photochemistry of hydrazoic acid (HN3)
11.3 Photochemistry of alkyl azides
11.4 Photochemistry of vinyl azides
11.5 Photochemistry of carbonyl azides and azide esters
11.6 Photochemistry of phenyl azide and its simple derivatives
11.7 Conclusion
11.8 Acknowledgements
11.9 References
Chapter 12: Organoazides and Transition Metals
Werner Thiel
12.1 Introduction
12.2 Metal complexes co-crystallized with an organoazide
12.3 Cationic metal complexes with organoazide containing anions
12.4 Metal complexes with ligands bearing a non-coordinating organoazide unit
12.5 Metal complexes with an intact, coordinating and linear organoazide ligand
12.6 Metal complexes with an intact, coordinating but bent organoazide ligand
12.7 Organoazides reacting with other metal bound ligands
12.8 References
PART 3: MATERIAL SCIENCES
Chapter 13: Azide-Containing High Energy Materials
Thomas Klapötke and Burkhard Krumm
13.1 Introduction
13.2 Organic Azides
13.3 Acknowledgments
13.4 References
Chapter 14: Azide Chemistry for Molecular Machines
Stephanie Durot, Julien Fry, Jean-Pierre Sauvage and Christian Took
14.1 Introduction
14.2 Purely organic rotaxanes and catenanes
14.3 Transition metal templated approaches
14.4 Conclusion
14.5 References
PART 4: APPLICATION IN BIOORGANIC CHEMISTRY
Chapter 15: Aza-Wittig Reaction in Natural Product Syntheses
Francisco Palacios, Concepción Alonso, Domitila Aparicio, Gloria Rubiales and Jesús M. de los Santo
15.1 Introduction
15.2 Intermolecular aza-Wittig reaction
15.3 Intramolecular aza-Wittig reaction
15.4 Conclusions
15.5 Acknowledgments
15.6 References
Chapter 16: Azides in Carbohydrate Chemistry
Henning S. G. Beckmann and Valentin Wittmann
16.1 Introduction
16.2 Synthesis of Azide-Containing Carbohydrates
16.3 Azides as Protecting Groups during Aminoglycoside Synthesis
16.4 Azides as Non-Participating Neighboring Groups in Glycosylations
16.5 Glycosyl Azides as Precursors for Glycosyl Amides
16.6 Synthesis of Glycoconjugates via Azide-Alkyne [3+2] Cycloaddition
16.7 Metabolic Oligosaccharide Engineering
16.8 References Key Word Index
"This book is timely and important - the first devoted entirely to azides to appear in 26 years. . . The editors are to be congratulated for attracting so many experts to produce an excellent work in a timely fashion that should find a place in all laboratories." (JACS, 2010)
