The Nitrile Imine 1,3-Dipole (eBook)

Properties, Reactivity and Applications

Craig Jamieson, Keith Livingstone (Autoren)

eBook Download: PDF

2020 | 1st ed. 2020
XI, 152 Seiten
Springer International Publishing (Verlag)
978-3-030-43481-6 (ISBN)

Infos

This book provides a comprehensive overview of the nitrilimine 1,3-dipole, from its initial discovery in 1959 to the most recent publications. Covering topics such as the core properties of the dipole and the various methods of synthesis available, it particularly highlights the diverse reactivity profile of the nitrilimine and its numerous applications in bioorthogonal and materials chemistry. The book is of interest to academic and industrial researchers working in this area and to those new to the field.

Craig Jamieson earned his B.Sc. (Hons) in Chemistry at the University of Glasgow in 1996. He pursued his Ph.D. studies under Professor R Ramage at the University of Edinburgh (1999). Following postdoctoral research under the supervision of Professor S V Ley at the University of Cambridge, in 2001 he was appointed as a Principal Scientist in GlaxoSmithKline's Discovery Medicinal Chemistry group, working on a range of exploratory medicinal chemistry programmes. In 2004, Dr Jamieson joined Organon Laboratories (later Merck Research Labs) as a Group Leader in the Medicinal Chemistry Department, with responsibility for hit to clinical candidate optimisation. In August 2010, he was appointed as a John Anderson Research Lecturer in Chemical Biology, based in the Department of Pure and Applied Chemistry at the University of Strathclyde.

Keith Livingstone completed his M.Chem in Chemistry with Drug Discovery at the University of Strathclyde (2016) under the supervision of Dr Craig Jamieson. Keith remained at Strathclyde and is currently in the final year of his doctoral studies with Dr Jamieson, which have also included two short research secondments at GlaxoSmithKline Medicines Research Centre Stevenage, and with Prof Ryan Gilmour at the Westfälische Wilhelms-Universität Münster.

Inhalt

Preface 5
Abstract 6
Contents 7
About the Authors 9
1 Nitrile Imines and Their Properties 10
1.1 History 10
1.2 Resonance Forms 11
1.3 Spectroscopy and Isolation 13
1.3.1 Ultraviolet 13
1.3.2 Infra-red 14
1.3.3 Nuclear Magnetic Resonance 14
1.3.4 Isolation of NI Compounds 14
References 18
2 The Generation of Nitrile Imine Derivatives 22
2.1 Hydrazonyl Halides 22
2.2 Hydrazonyl Psuedohalides 26
2.3 Hydrazones 27
2.4 Tetrazoles 28
2.4.1 Thermolysis 29
2.4.2 Photolysis 31
2.5 Sydnones 37
2.6 Other Sources 39
References 41
3 The Reactivity of Nitrile Imines 45
3.1 1,3-Dipolar Cycloaddition 45
3.1.1 Regioselectivity 46
3.1.2 Rate of Reaction 47
3.1.3 Carbon-Carbon Double Bonds 51
3.1.4 Carbon-Carbon Triple Bonds 58
3.1.5 Carbon-Nitrogen Bonds 60
3.1.6 Carbon-Sulfur Bonds 64
3.1.7 Carbon-Oxygen Bonds 66
3.1.8 Heterocycles 67
3.1.9 Other Substrates 69
3.2 Nucleophiles 70
3.2.1 Alcohols 71
3.2.2 Amines 72
3.2.3 Thiols 74
3.2.4 Carboxylic Acids 75
3.2.5 Isocyanides 77
3.2.6 Phosphines 78
3.2.7 Boronic Acids 80
3.2.8 Enamines and Enol Ethers 80
3.3 Dimerisation 83
3.4 Intramolecular Rearrangements 86
3.5 Carbenic Nitrile Imines 90
3.6 Decomposition 93
References 94
4 Applications of Nitrile Imine Derivatives 106
4.1 General Synthesis 106
4.1.1 Biomolecules and Natural Products 107
4.1.2 Medicinally Relevant Compounds 108
4.2 Bioorthogonal Chemistry 109
4.2.1 Protein Ligation 115
4.2.2 Bioconjugative Reactions 121
4.2.3 Peptide Stapling 123
4.2.4 Chemosensors 124
4.2.5 Other Applications 126
4.3 Materials Chemistry 127
4.3.1 Polymer Synthesis 127
4.3.2 Polymer Cross-Linking 129
4.3.3 Reactions with Carbon Allotropes 134
4.3.4 Surface Chemistry 141
References 149
5 Conclusions 158
References 158

Produkt-Details

• Erscheint lt. Verlag: 25.3.2020
• Zusatzinfo: XI, 152 p. 218 illus., 120 illus. in color.
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Biologie
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Wirtschaft
• Schlagworte: 1,3-Dipolar Cycloaddition • 1,3-Dipoles • 2,5-Tetrazoles • Bioorthogonal chemistry • nitrile imines • Nitrilium Betaine • photolysis • Protein Structure
• ISBN-10: 3-030-43481-8 / 3030434818
• ISBN-13: 978-3-030-43481-6 / 9783030434816