Оглавление
Группа авторов. Methodologies in Amine Synthesis
Table of Contents
List of Tables
List of Illustrations
Guide
Pages
Methodologies in Amine Synthesis. Challenges and Applications
Preface
1 Substitution‐type Electrophilic Amination Using Hydroxylamine‐Derived Reagents
1.1 Introduction
1.2 Cu‐Catalyzed Reactions
1.3 Electrophilic Amination Reactions Catalyzed by Other Transition Metals
1.4 Electrophilic Amination with Hydroxylamine‐derived Metallanitrenes
1.5 Transition‐Metal‐Free Electrophilic Amination Reactions
1.6 Conclusion
References
2 Remote Functionalizations Using Nitrogen Radicals in H‐Atom Transfer (HAT) Reactions
2.1 Introduction
2.2 Intramolecular 1,5‐H‐Atom Transfer (1,5‐HAT)
2.3 Photoinduced Strategies. 2.3.1 Reductive Strategies
2.3.1.1 1,5‐HAT via Iminyl Radicals
2.3.1.2 1,5‐HAT via Amidyl and Sulfamidyl Radicals
2.3.2 Oxidative Strategies. 2.3.2.1 1,5‐HAT via Iminyl Radicals
2.3.2.2 1,5‐HAT via Amidyl and Sulfamidyl Radicals
2.3.3 Photoinduced Bond Homolysis
2.4 Thermal Strategies
2.5 Summary and Conclusions
References
3 Radical‐Based C—N Bond Formation in Photo/Electrochemistry
3.1 Introduction
3.2 C—N Bond Formation via N‐radical Species Addition
3.2.1 Radical Addition to C—C Double/Triple Bonds. 3.2.1.1 Amidyl Radical Addition
3.2.1.2 Hydrazonyl Radical Addition
3.2.1.3 Aminium Radical Cation Addition
3.2.2 Radical Species Addition to Aromatic Rings
3.3 Amination via N‐atom Nucleophilic Addition
3.3.1 Aromatic C(sp2)—H Bond Amination
3.3.2 Olefinic C(sp2)—H Bond Amination
3.3.3 Activated C(sp3)—H Bond Amination
3.3.3.1 Benzylic C(sp3)—H Bond Amination
3.3.3.2 N‐α‐C(sp3)—H Bond Amination
3.4 Amination via Radical Cross‐coupling
3.4.1 Aryl C(sp2)—N Bond Formation via Radical Cross‐coupling
3.4.1.1 Aryl C(sp2)—N Bond Formation Using Diarylamines
3.4.1.2 Aryl C(sp2)—N Bond Formation Using Azoles
3.4.2 Other C—N Bond Formation via Radical Cross‐coupling
3.5 Summary and Conclusions
References
4 Propargylamines: Recent Advances in Asymmetric Synthesis and Use as Chemical Tools in Organic Chemistry
4.1 Introduction
4.2 Metal‐Catalyzed Asymmetric Synthesis of Propargylamines. 4.2.1 Enantioselective A3 Coupling
4.2.1.1 Enantioselective A3 Coupling Involving Primary Amines
4.2.1.2 Enantioselective A3 Coupling Involving Secondary Amines
4.2.2 Enantioselective Propargylic Amination of Propargylic Esters with Amines
4.2.3 Cu‐Catalyzed Enantioselective Ring Opening of Alkynyl‐Substituted Epoxides/Lactones/Carbonates
4.2.4 Enantioselective Addition of Terminal Alkynes to Enamines/Enamides
4.2.5 Rh/Ru‐Catalyzed Enantioselective Hydrogenation of Alkynyl‐Substituted Enamides/Imines
4.2.6 Enantioselective C–H Activation: Synthesis of Cyclic Propargylamines
4.3 Enzymatic Synthesis of Propargylamines
4.4 Photoredox Synthesis of Propargylamines
4.5 Organocatalyzed Asymmetric Synthesis of Propargylamines
4.6 Propargylamines as Building Blocks in the Synthesis of Heterocycles
4.6.1 Synthesis of Pyrroles from Propargylamines
4.6.2 Synthesis of Pyrrolines from Propargylamines
4.6.3 Synthesis of Pyridines from Propargylamines
4.6.4 Synthesis of Quinolines from Propargylamines
4.6.5 Synthesis of Oxazoles from Propargylamines
4.6.6 Synthesis of Thiazoles from Propargylamines
4.7 Conclusions
References
5 Transition‐Metal‐Catalyzed Chiral Amines Synthesis
5.1 Introduction
5.2 Asymmetric Reductive Amination
5.3 Asymmetric Hydroamination
5.4 Asymmetric Hydroaminoalkylation
5.5 Asymmetric Hydroaminomethylation
5.6 Coupling on a Chiral Metal Center
5.7 Conclusion
References
6 Industrial Relevance of Asymmetric Organocatalysis in the Preparation of Chiral Amine Derivatives
6.1 Introduction
6.2 Organocatalysis in Manufacture: Representative Examples
6.3 Case Studies. 6.3.1 Pregabalin
6.3.1.1 Pathway A: Desymmetrization of Glutaric Anhydride 53
6.3.1.2 Pathway B: Addition of an Amino α‐Carbanion 55 to Michael Acceptors
6.3.1.3 Pathway C: Addition of Acetate Enolate Equivalents to Nitroalkene 56
6.3.2 Bicyclic α‐Amino Acid Core of Telaprevir
6.3.3 5‐(Trifluoromethyl)‐2‐isoxazolines as Antipest Agents
6.4 Summary and Conclusions
References
Note
7 Biocatalytic Synthesis of Chiral Amines Using Oxidoreductases
7.1 Introduction
7.2 Amine Oxidases. 7.2.1 Introduction
7.2.2 (S)‐Selective Amine Oxidases. 7.2.2.1 Monoamine Oxidase from Aspergillus niger
7.2.2.2 Directed Evolution of MAO‐N
7.2.2.3 Synthetic Applications and Cascades
7.2.2.4 Monoamine Oxidase from Pseudomonas monteilii ZMU‐T01
7.2.2.5 Cyclohexylamine Oxidase from Brevibacterium oxydans (CHAO)
7.2.3 (R)‐Selective Amine Oxidases
7.2.3.1 D‐Amino Acid Oxidase (pkDAO)
7.2.3.2 6‐Hydroxy-D-nicotine Oxidase (6‐HDNO) from Arthrobacter nicotinovorans
7.3 Amine Dehydrogenases. 7.3.1 Introduction
7.3.2 Discovery and Engineering of AmDH. 7.3.2.1 Leucine Dehydrogenase
7.3.2.2 Phenylalanine Dehydrogenase and Chimeric Amine Dehydrogenase
7.3.2.3 Native Amine Dehydrogenase
7.3.3 Synthetic Applications of AmDH. 7.3.3.1 Primary Amine Synthesis with Engineered AmDH
7.3.3.2 Primary Amine Synthesis with Natural AmDH
7.3.3.3 Substrate Promiscuity in AmDH. Reductive Aminase Activity
Amino Alcohol Synthesis
7.3.3.4 Cascade Reactions that Use AmDH
Biocatalytic Hydrogen Borrowing
Other Multienzyme Cascades
Chemoenzymatic Cascades
7.4 Imine Reductases. 7.4.1 From Biosynthesis to Biocatalysis
7.4.2 Biocatalytic Application of Imine Reductases
7.4.2.1 IREDs in Cascade and Chemoenzymatic Synthesis
7.4.3 IRED Engineering
7.4.4 Imine Reductases Catalyzing Reductive Amination
7.4.5 Imine Reductase‐Catalyzed Amine Alkylation Cascades
7.4.6 Engineering of Reductive Aminases
7.5 Engineered Cytochrome P450s
7.6 Conclusions and Perspectives
References
8 Engineering Functional Nanomaterials Through the Amino Group
Abbreviations
8.1 Introduction
8.2 Quantification of Nanomaterial‐Bound Amino Groups
8.3 Exploiting Amino Compounds for the Functionalization of Carbon‐Based Nanomaterials. 8.3.1 Historical Backgrounds: Allotropes of Carbon
8.3.2 Use of Amines for the Functionalization of Carbon Nanostructures
8.3.3 Other Functionalization Procedures of Common Carbon Nanostructures
8.3.4 Exfoliation of Graphite with Melamine
8.3.5 Other Carbon Nanomaterials
8.3.5.1 Carbon Nanohorns
8.3.5.2 Carbon Nanodiamonds
8.3.5.3 Carbon Nano‐onions
8.3.6 Amino‐Functionalized Carbon‐Based Nanomaterials for Analytical Applications
8.4 Amines in the Synthesis and Functionalization of Carbon Dots
8.4.1 Amines as CD Constituents
8.4.2 Amine‐Rich CDs from Arginine and Ethylenediamine (NCDs)
8.4.2.1 One‐Pot Functionalization of NCDs
8.4.2.2 Postfunctionalization of NCDs
8.4.2.3 Use of CD‐Supported Amines in Organocatalysis
8.5 Amines for the Engineering of Hybrid Organic–Inorganic Nanomaterials
8.5.1 Amines as Head Groups or End Groups on Self‐assembled Monolayers on Flat Surfaces
8.5.2 Alkylamines in the Preparation of Semiconductor Quantum Dots
8.5.2.1 Sulfur–Amine and Selenium–Amine Systems
8.5.2.2 Capping Ligands for Quantum Dots and Ligand Exchange by Amines
8.5.3 Alkylamines as Reagents for the Synthesis and Passivation of Metal Nanoparticles. 8.5.3.1 Alkylamines as Capping Agents for Metal Nanoparticles
8.5.3.2 Displacement of Amines from the Surface of Metal Nanoparticles
8.5.4 Amines on the Outer Surface of Organic–inorganic Hybrid Nanoparticles
8.5.5 Postfunctionalization of Amine‐Terminated Organic–Inorganic Hybrid Nanoparticles
References
9 Recent Advances in the Synthesis of Nitrogen Compounds from Biomass Derivatives
9.1 Introduction
9.2 Synthesis of Nitrogen Compounds from Chitin and Its Derivatives
9.3 Synthesis of Amines and Formamides from α‐Amino Acids
9.4 Synthesis of Nitrogen Compounds from Cellulosic Biomass Derivatives
9.5 Synthesis of Nitrogen Compounds from Lignin Derivatives
9.6 Synthesis of Nitrogen Compounds from Triglycerides and Fatty Alcohols
9.7 Conclusion
References
10 Recent Advances in the Synthesis of Arylamines in the Light of Application in Pharmaceutical and Chemical Industry
10.1 Modern Approaches to Transition‐Metal‐Catalyzed C–N Coupling in Industry. 10.1.1 Introduction
10.1.2 Transition‐Metal‐Catalyzed C—N‐Bond Formation
10.1.2.1 Ullmann‐Type Amination
Mechanistic Studies
Catalysts and Variants of the Ullmann Coupling for the Formation of C—N Bonds
Recent Applications on Industrial Scale of Ullmann and Chan–Lam Coupling
10.1.2.2 Buchwald–Hartwig Amination
Mechanistic Studies
Catalyst Design
Recent Applications in Industry
10.2 New Methodologies in the Synthesis of Arylamines on the Brink of Industrial Application. 10.2.1 Introduction
10.2.2 Catalytic C–H Amination
10.2.2.1 Catalytic C–H Amination under Standard Conditions
10.2.2.2 Photoredox Catalysis
10.2.2.3 Electrochemical Approaches
10.2.3 Decarboxylative Aryl Amination
10.2.4 Nickel‐Catalyzed C–N Coupling
10.2.5 Other Metal‐Catalyzed Cross‐Couplings
10.2.6 Reductive Amination
10.2.7 Hydroamination
10.2.8 Summary and Conclusions
10.3 Advances to Arylamine Formation Using Intensified and More Sustainable Process Technologies. 10.3.1 Introduction
10.3.2 Flow Chemistry
10.3.2.1 Pd‐Catalyzed C—N Bond Forming Reaction
10.3.2.2 Nucleophilic Aromatic Substitution
10.3.2.3 Telescoped Sequence of Nitration and Hydrogenation in Flow Synthesis
10.3.2.4 Chan–Lam Coupling
10.3.3 Immobilization of Catalysts/Supported Catalysts
10.3.4 Personal Accounts from Contract Manufacturing Companies on Utility of Modern Flow Amination Methods
10.4 Miscellaneous Aspects of Aromatic Amination Reactions in the World of Active Pharmaceutical Ingredients. 10.4.1 Cohort of Concerns and its Regulatory Impact on Amine‐Based Active Pharmaceutical Compounds
10.4.2 Role of Control of Elemental Impurities in Human Pharma Applications
10.4.3 Transition Metal Accounting
10.4.4 Recycling of Metals, Ligands, and Other Cost Drivers of Aromatic Amination
10.4.5 Regulatory Requirements for the Submission of a Catalytic Reaction in a New Drug Application
References
Index
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