Organic Azides

Stefan Brase was born in Kiel, Germany, in 1967 and studied chemistry in Gottingen, Bangor (UK) and Marseille (France). In 1995, he obtained his doctorate after working with Armin de Meijere at the University of Gottingen. After post-doctoral appointments at Uppsala University, Sweden (J.-E. Backvall) 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 Brase 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.

* 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 SharplessPrefaceList of ContributorsAbbreviationsPART 1: SYNTHESIS + SAFETYChapter 1: Safety Issues about Azide CompoundsThomas Keicher and Stefan Löbbecke1.1 Introduction1.2 Properties that impose restrictions on lab-scale handling of azides1.3 Laboratory safety instructions for the small scale synthesis of azido compounds1.4 Analyzing safety-related properties of azides1.5 ReferencesChapter 2: Large Scale Preparation of AzidesJürgen Haase2.1 Introduction2.2 Precursor azides, technical production and properties2.3 Examples for the use of azides on a technical scale2.4 The future of commercial-scale azide chemistry2.5 ReferencesChapter 3: Synthesis of AzidesTeresa M. V. D. Pinho e Melo3.1 Introduction3.2 Synthesis of Alkyl Azides3.3 Synthesis of Aryl Azides3.4 Synthesis of Acyl Azides3.5 ReferencesChapter 4: Azides by Hydroazidination ReactionsJérôme Waser and Erick Carreira4.1 Introduction4.2 Conjugate Addition of Hydrazoic Acid and Its Derivatives4.3 Addition of Hydrazoic Acid and its Derivatives to Non-Activated Olefins4.4 Cobalt-Catalyzed Hydroazidation4.5 Conclusion4.6 ReferencesPART 2: REACTIONSChapter 5: The Chemistry of Vinyl, Allenyl, and Ethynyl AzidesKlaus Banert5.1 Introduction and Early Synthetic Methods for Vinyl Azides5.2 Routes to Vinyl Azides Developed in the Period 1965 - 19705.3 New Methods to Prepare Vinyl Azides5.4 Reactions of Vinyl Azides5.5 The Chemistry of Allenyl Azides5.6 Generation of Ethynyl Azides5.7 Conclusion5.8 ReferencesChapter 6: Small Rings by Azide ChemistryThomas Gilchrist and Maria Alves6.1 Introduction6.2 2H-Azirines6.3 Aziridines6.4 Triaziridines6.5 Azetidinones6.6 ReferencesChapter 7: Schmidt Rearrangement Reactions with Alkyl AzidesScott Grecian and Jeffrey Aubé7.1 Introduction and Early Attempts (1940-1960)7.2 Schmidt reactions of alkyl azides with carbonyl compounds7.3 Schmidt reactions of alkyl azides with carbocations7.4 Metal-mediated Schmidt reactions of alkyl azides with alkenes and alkynes7.5 Reactions of alkyl azides with a,b-unsaturated ketones7.6 Reactions of alkyl azides with epoxides7.7 Combined Schmidt rearrangement cascade reactions7.8 Schmidt rearrangements in the total synthesis of natural products7.9 Schmidt rearrangements of alkyl azides in the synthesis of interesting non-natural products7.10 Schmidt rearrangements of hydroxyalkyl azides toward biologically relevant compounds7.11 Final Comments7.12 Acknowledgments7.13 ReferencesChapter 8: Radical Chemistry with AzidesCiril Jimeno and Philippe Renaud8.1 Introduction8.2 Addition of the azidyl radical onto alkenes8.3 Azidation of carbon centered radicals8.4 Aminyl and amidyl radicals via reduction of azides8.5 Fragmentation reaction of alpha-azidoalkyl radicals8.6 ConclusionsChapter 9: Cycloaddition Reactions with AzidesC. Schilling, N. Jung and Stefan Bräse9.1 Huisgen 1,3-dipolar cycloaddition9.2 Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC)9.3 Acceleration of the Click Reaction9.4 Copper-free Click chemistry9.5 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 tetrazoles9.8 Click chemistry for the synthesis of dihydrotriazoles9.9 Cycloaddition reactions with azides to give thiatriazoles9.10 ReferencesChapter 10: Dipolar Cycloaddition Reactions in Peptide ChemistryChristian Wenzel Tornøe and Morten Meldal10.1 Introduction10.2 Amino Acid Derivatives by DCR10.3 Peptide Backbone Modifications by DCR10.4 Other Peptide Modifications by DCR10.5 Macrocyclization by DCR10.6 Dendrimers and Polymers10.7 Isotopic Labeling by DCR10.8 Perspective10.9 ReferencesChapter 11: Photochemistry of Azides: The Azide/Nitrene InterfaceMatthew Platz and Nina Gritsan11.1 Introduction11.2 Photochemistry of hydrazoic acid (HN3)11.3 Photochemistry of alkyl azides11.4 Photochemistry of vinyl azides11.5 Photochemistry of carbonyl azides and azide esters11.6 Photochemistry of phenyl azide and its simple derivatives11.7 Conclusion11.8 Acknowledgements11.9 ReferencesChapter 12: Organoazides and Transition MetalsWerner Thiel12.1 Introduction12.2 Metal complexes co-crystallized with an organoazide12.3 Cationic metal complexes with organoazide containing anions12.4 Metal complexes with ligands bearing a non-coordinating organoazide unit12.5 Metal complexes with an intact, coordinating and linear organoazide ligand12.6 Metal complexes with an intact, coordinating but bent organoazide ligand12.7 Organoazides reacting with other metal bound ligands12.8 ReferencesPART 3: MATERIAL SCIENCESChapter 13: Azide-Containing High Energy MaterialsThomas Klapötke and Burkhard Krumm13.1 Introduction13.2 Organic Azides13.3 Acknowledgments13.4 ReferencesChapter 14: Azide Chemistry for Molecular MachinesStephanie Durot, Julien Fry, Jean-Pierre Sauvage and Christian Took14.1 Introduction14.2 Purely organic rotaxanes and catenanes14.3 Transition metal templated approaches14.4 Conclusion14.5 ReferencesPART 4: APPLICATION IN BIOORGANIC CHEMISTRYChapter 15: Aza-Wittig Reaction in Natural Product SynthesesFrancisco Palacios, Concepción Alonso, Domitila Aparicio, Gloria Rubiales and Jesús M. de los Santo15.1 Introduction15.2 Intermolecular aza-Wittig reaction15.3 Intramolecular aza-Wittig reaction15.4 Conclusions15.5 Acknowledgments15.6 ReferencesChapter 16: Azides in Carbohydrate ChemistryHenning S. G. Beckmann and Valentin Wittmann16.1 Introduction16.2 Synthesis of Azide-Containing Carbohydrates16.3 Azides as Protecting Groups during Aminoglycoside Synthesis16.4 Azides as Non-Participating Neighboring Groups in Glycosylations16.5 Glycosyl Azides as Precursors for Glycosyl Amides16.6 Synthesis of Glycoconjugates via Azide-Alkyne [3+2] Cycloaddition16.7 Metabolic Oligosaccharide Engineering16.8 References Key Word Index