Discover a comprehensive overview of efficient synthetic routes to an important compound class in organic and pharmaceutical chemistry
Methodologies in Amine Synthesis: Challenges and Applications delivers powerful and state-of-the-art methods for the efficient preparation of amines. The text summarizes recent advances in the electrophilic amination reaction, hydroamination, C-H amination and newly developed photocatalytic approaches. The distinguished editor has included resources that discuss organocatalytic and enzymatic routes to the generation of amines under mild and environmentally friendly conditions.
The book also highlights the relevance of the amino function in bioactive molecules, drugs, and smart materials, as well as the palladium-catalyzed aromatic amination reaction. It presents efficient and practical synthetic methods, highlights the opportunities and challenges associated with each, and discusses their possible applications in pharmaceutical chemistry and materials science.
Edited by the expert who wrote Modern Amination Methods and Amino Group Chemistry, the book includes a breadth and depth of material essential to the practice of academic and industrial chemists working in organic synthesis and catalysis. Readers will also benefit from the inclusion of:
- A thorough introduction to new openings and perspectives in the electrophilic amination
- Discussions of asymmetric catalysed hydroaminomethylation and amino organocatalysis
- A treatment of the synthetic application of transaminase or MAO biocatalysis to the synthesis of amines
- An exploration of recent developments in C-H amination, as well as photocatalytic approaches to the synthesis of amines
- An examination of primary amines from renewable bio-based resources
Perfect for organic, natural product, catalytic, medicinal, and polymer chemists, Methodologies in Amine Synthesis: Challenges and Applications will also earn a place in the libraries of materials scientists and chemists working with organometallics who desire a one-stop reference edited by a well-known expert in the field.
Table of Contents
Preface xi
1 Substitution-type Electrophilic Amination Using Hydroxylamine-Derived Reagents 1
Zhe Zhou and László Kürti
1.1 Introduction 1
1.2 Cu-Catalyzed Reactions 2
1.3 Electrophilic Amination Reactions Catalyzed by Other Transition Metals 15
1.4 Electrophilic Amination with Hydroxylamine-derived Metallanitrenes 18
1.5 Transition-Metal-Free Electrophilic Amination Reactions 22
1.6 Conclusion 28
2 Remote Functionalizations Using Nitrogen Radicals in H-Atom Transfer (HAT) Reactions 31
Ji Hye Kim, Elizabeth M. Dauncey and Daniele Leonori
2.1 Introduction 31
2.2 Intramolecular 1,5-H-Atom Transfer (1,5-HAT) 31
2.3 Photoinduced Strategies 34
2.4 Thermal Strategies 46
2.5 Summary and Conclusions 50
3 Radical-Based C-N Bond Formation in Photo/Electrochemistry 53
Binbin Huang, Yating Zhao and Wujiong Xia
3.1 Introduction 53
3.2 C-N Bond Formation via N-radical Species Addition 54
3.3 Amination via N-atom Nucleophilic Addition 77
3.4 Amination via Radical Cross-coupling 90
3.5 Summary and Conclusions 98
4 Propargylamines: Recent Advances in Asymmetric Synthesis and Use as Chemical Tools in Organic Chemistry 103
Fei Zhao, Seong-Heun Kim and Daniele Castagnolo
4.1 Introduction 103
4.2 Metal-Catalyzed Asymmetric Synthesis of Propargylamines 104
4.3 Enzymatic Synthesis of Propargylamines 126
4.4 Photoredox Synthesis of Propargylamines 130
4.5 Organocatalyzed Asymmetric Synthesis of Propargylamines 134
4.6 Propargylamines as Building Blocks in the Synthesis of Heterocycles 137
4.7 Conclusions 150
5 Transition-Metal-Catalyzed Chiral Amines Synthesis 155
Anton Cunillera, Carmen Claver, Cyril Godard, Martine Urrutigoïty and Philippe Kalck
5.1 Introduction 155
5.2 Asymmetric Reductive Amination 156
5.3 Asymmetric Hydroamination 162
5.4 Asymmetric Hydroaminoalkylation 168
5.5 Asymmetric Hydroaminomethylation 171
5.6 Coupling on a Chiral Metal Center 176
5.7 Conclusion 177
6 Industrial Relevance of Asymmetric Organocatalysis in the Preparation of Chiral Amine Derivatives 187
Luca Bernardi, Armando Carlone and Francesco Fini
6.1 Introduction 187
6.2 Organocatalysis in Manufacture: Representative Examples 189
6.3 Case Studies 200
6.4 Summary and Conclusions 230
7 Biocatalytic Synthesis of Chiral Amines Using Oxidoreductases 243
Sebastian C. Cosgrove, Jeremy I. Ramsden, Juan Mangas-Sanchez and Nicholas J. Turner
7.1 Introduction 243
7.2 Amine Oxidases 243
7.3 Amine Dehydrogenases 252
7.4 Imine Reductases 262
7.5 Engineered Cytochrome P450s 270
7.6 Conclusions and Perspectives 274
8 Engineering Functional Nanomaterials Through the Amino Group 285
Giacomo Filippini, Paolo Pengo, Susanna Bosi, Giulio Ragazzon, Lucia Pasquato and Maurizio Prato
8.1 Abbreviations 285
8.1 Introduction 287
8.2 Quantification of Nanomaterial-Bound Amino Groups 288
8.3 Exploiting Amino Compounds for the Functionalization of Carbon-Based Nanomaterials 290
8.4 Amines in the Synthesis and Functionalization of Carbon Dots 309
8.5 Amines for the Engineering of Hybrid Organic-Inorganic Nanomaterials 316
9 Recent Advances in the Synthesis of Nitrogen Compounds from Biomass Derivatives 341
Ana C. Fernandes
9.1 Introduction 341
9.2 Synthesis of Nitrogen Compounds from Chitin and Its Derivatives 341
9.3 Synthesis of Amines and Formamides from Alpha-Amino Acids 345
9.4 Synthesis of Nitrogen Compounds from Cellulosic Biomass Derivatives 348
9.5 Synthesis of Nitrogen Compounds from Lignin Derivatives 366
9.6 Synthesis of Nitrogen Compounds from Triglycerides and Fatty Alcohols 370
9.7 Conclusion 373
10 Recent Advances in the Synthesis of Arylamines in the Light of Application in Pharmaceutical and Chemical Industry 377
Dino Berthold, Alexander M. Haydl, Joyce C. Leung, Ulrich Scholz, Qing Xiao and Zhibin Zhu
10.1 Modern Approaches to Transition-Metal-Catalyzed C-N Coupling in Industry 377
10.2 New Methodologies in the Synthesis of Arylamines on the Brink of Industrial Application 388
10.3 Advances to Arylamine Formation Using Intensified and More Sustainable Process Technologies 424
10.4 Miscellaneous Aspects of Aromatic Amination Reactions in theWorld of Active Pharmaceutical Ingredients 431
References 435
Index 445
