Organic Azides

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