Copper in N-Heterocyclic Chemistry

Description

Copper in N-Heterocyclic Chemistry provides an overview of copper-catalyzed synthesis and functionalization of N-heterocyclic compounds, covering all recent developments in a way that is ideal for researchers and students working in the area of synthetic organic chemistry and medicinal chemistry. The book explores N-heterocyclic compounds as unique structural units in the development of natural products and pharmaceuticals, along with the remarkable progress made in the area of high atom economic strategies, and more recently, copper-catalyzed C-H activation and its applications in organic synthesis. Readers will find troubleshooting protocols, as well as the advantages and limitations of each method discussed. As copper catalysts show versatile chemical reactivity in many aspects, including their oxidation states 0–3 are accessible and their ability to facilitate bond formations due to their ability to serve as Lewis acids, oxidizing agents and catalysts, this book is an ideal resource on the topics explored. Front matter Copyright Contributors About the editor Preface 1. Copper-catalyzed synthesis of aziridines 1 Introduction 2 Asymmetric nucleophilic addition to 2H-azirines 3 Reaction of aziridines and oxaziridines 3.1 Alkylation of nonstabilized aziridinyl-grignard reagents 3.2 Alkylation of aziridinylmethyl tosylate using grignard reagents 3.3 N-Functionalization of aziridines 3.4 Nitrogen radical cyclization reactions of oxaziridines 4 Cycloaddition reactions 5 Cyclization reaction/Baldwin rearrangement 6 Copper-catalyzed C–H amination reaction 7 Aziridination via intramolecular SN2 substitution 8 Aziridination of imines via carbene transfer 8.1 Aziridination of imines by diazocarbonyl derived carbenes 8.2 Sulfur ylide-mediated aziridination of imines 9 Aziridination of olefins via nitrene transfer 9.1 Iminoiodinanes as nitrene precursors 9.2 Sulfonamides, sulfamates, sulfonimidamides, hydroxylamine-o-sulfonic acid (HOSA), o-arylsulfonylhydroxylamines, and n-tosyloxycarbamates as nitrene precursors Acknowledgments References 2. Copper catalysis for imidazoles and pyrazoles 1 Introduction 2 Synthesis of imidazole and its congener using copper catalyst 3 Synthesis of benzimidazole and its congener by using copper catalyst 4 Synthesis of pyrazole and its congener by using copper catalyst 5 Conclusion References 3. Copper catalysis in the synthesis of 1,2,3-triazoles and tetrazoles 1 Introduction 2 Properties of 1,2,3-triazoles and tetrazoles 2.1 Acid and base properties 2.2 Triazoles as pharmacophores—Intermolecular interactions with biological molecules 2.3 Aromaticity 3 Synthetic strategies for the synthesis of 1,2,3-triazole and tetrazole nucleus 3.1 Metal-free synthesis 4 Recent developments in copper catalysis in the synthesis of 1,2,3-triazoles and tetrazoles 4.1 Copper catalysis in the synthesis of tetrazoles and N2-substituted 1,2,3-triazoles References 4. Copper catalysis for pyridines and pyrimidines 1 Introduction 1.1 Cu-catalyzed synthesis of pyridines 1.2 Pyridines from the reaction between azadienes and acetylenes 1.3 Pyridines from β-enaminones 1.4 Pyridines from the Cu(II)-catalyzed coupling of methylene carbonyls with amines 1.5 Pyridines from the cyclization of oximes and their derivatives 1.6 Pyridines from the intramolecular cyclization of azides 1.7 Cu-catalyzed pyrimidine synthesis 1.8 Pyrimidines from the oxidative dehydrogenation of alcohols, ketones, amino acids, and nitriles 1.9 Pyrimidines from the lewis acid activation of amidines, propargylic alcohols, nitriles, and aziridines 1.10 Pyrimidine synthesis via sonogashira and ullman couplings and other reactions of metal-acetylides 1.11 Pyrimidine synthesis via the cycloaddition of ketenimines 2 Conclusion References 5. Copper catalysis for triazines 1 Introduction 2 Synthesis 2.1 Synthesis of 1,3,5-triazines 2.2 Synthesis of 1,2,4-triazines 2.3 Synthesis of 1,2,3-triazines 3. Modification of triazines 3.1 Sandmeyer reaction 3.2 Sonogashira reaction 3.3 Liebeskind-srogl coupling 3.4 Ullmann and Ullmann-type reaction 3.5 Chan-Lam coupling 3.6 Silyl-Hilbert-Johnson reaction (Vorbrüggen reaction) 3.7 Other reactions 4. Conclusion Acknowledgment References 6. Copper catalysis for pyrazines and quinoxalines 1 Introduction 2 Synthesis of quinoxaline and its congener using copper catalyst 2.1 Synthesis of quinoxaline from diamine 2.2 Synthesis of quinoxaline moiety from alkynes 2.3 Synthesis of quinoxaline moiety using sodium azide 2.4 Synthesis of quinoxaline-fused heterocyclic molecules 3 Synthesis of pyrazine and its congener using copper catalyst 3.1 Synthesis of pyrazine by conventional method 3.2 Synthesis of unsymmetrical substituted pyrazine derivatives 3.3 Synthesis of substituted pyrazine derivatives 3.4 Synthesis of N-fused pyrazine derivative 4 Conclusion Acknowledgement References 7. Copper catalysis for the synthesis of quinolines and isoquinolines 1 Introduction 2 Copper-catalyzed synthesis of quinolines 2.1 Intramolecular reactions 2.2 Synthesis of quinolines involving two bond-forming reactions 2.3 Synthesis of quinolines via multicomponent reactions 2.4 Synthesis of fused quinolines 3 Copper-catalyzed synthesis of isoquinolines 3.1 Intramolecular reactions 3.2 Synthesis of isoquinolines involving two bond-forming reactions 3.3 Synthesis of isoquinolines via multicomponent reactions 3.4 Synthesis of fused isoquinolines 4 Summary References 8. Copper-mediated synthesis of quinazolines and related benzodiazines 1 Introduction 2 Synthesis of quinazoline derivatives by Cu-mediated condensation/oxidation 3 Synthesis of quinazoline derivatives via Ullmann-Goldberg reaction 4 Synthesis of quinazoline derivatives using miscellaneous methods 5 Synthesis of polycyclic quinazoline derivatives 6 Cu-mediated synthesis of other benzodiazines 7 Modification of quinazoline and quinoxaline scaffolds 8 Conclusion References 9. Copper catalysis for large rings 1 Introduction 2 Copper-catalyzed “click” reaction for the construction of aza-macrocycles 3 Copper-catalyzed N-arylation for the construction of aza-large ring 4 Copper-catalyzed atom transfer radical cyclization reactions 5 Conclusions and outlook References 10. Copper catalysis for saturated N-heterocycles via C–H functionalization 1 Introduction 2 Four-membered saturated N-heterocycles 3 Five-membered saturated N-heterocycles 3.1 Pyrrolidine 3.2 Pyrrolidone 3.3 Dihydrooxazole 3.4 Oxazolidinone 3.5 Dihydroimidazole 3.6 Indoline 3.7 Oxindole 3.8 Isatin 3.9 Isoindolinone 3.10 Succinimide 4 Six-membered saturated N-heterocycles 4.1 Benzoxazine 4.2 Dihydro-oxazinone 4.3 Piperidine 4.4 Tetrahydroquinolines 5 Seven-membered saturated N-heterocycles 6 Summary References 11. Pursuit for simple and efficient ligands promoting copper-catalyzed Ullmann type reactions for N-aryl heterocycles and aromatic amines 1 Introduction 2 Ligands in Ullmann reaction: Mechanism for C-N bond formation 3 Ligands in C-N bond formation 3.1 N-Arylation of heterocycles 3.2 N-Arylation of anilines 4 Ligands for promoting Cu-catalyzed C-N bond formation in material and drug development 5 Conclusions Acknowledgments References 12. Solid supported copper for N-heterocycles 1 Supported nanocatalysts 2 Catalysis by Cu-MOFs 3 Supported copper salts and complexes Acknowledgments References 13. Copper catalysis for biologically active N-heterocycles 1 Introduction 2 Synthesis of N-heterocycles and their biological activities 3 Conclusion References Index