| | Contents | |
| | | |
| |
| | Preface | XI |
| | List of Contributors | XIII |
| 1 | Simple Molecules, Highly Efficient Amination
Shunsuke Chiba and Koichi Narasaka | 1 |
| 1.1 | Introduction | 1 |
| 1.2 | Hydroxylamine Derivatives | 1 |
| 1.2.1 | O-Sulfonylhydroxylamine | 1 |
| 1.2.2 | O-Phosphinylhydroxylamine | 4 |
| 1.2.3 | O-Acylhydroxylamine | 5 |
| 1.2.4 | O-Trimethylsilylhydroxylamine | 6 |
| 1.2.5 | Experimental Procedures | 7 |
| 1.3 | Oxime Derivatives | 9 |
| 1.3.1 | Synthesis of Primary Amines by Electrophilic Amination of Carbanions | 9 |
| 1.3.2 | Experimental Procedures | 13 |
| 1.4 | Azo Compounds | 15 |
| 1.4.1 | Azodicarboxylates | 15 |
| 1.4.1.1 | Allylic Amination through Ene-Type Reactions | 15 |
| 1.4.1.2 | Hydrohydrazination of Alkenes | 16 |
| 1.4.2 | Arylazo Sulfones | 19 |
| 1.4.3 | Experimental Procedures | 20 |
| 1.5 | Oxaziridine Derivatives | 23 |
| 1.5.1 | Electrophilic Amination of Carbon Nucleophiles | 23 |
| 1.5.2 | Amination of Allylic and Propargylic Sulfides by Use of a Ketomalonate-Derived Oxaziridine | 23 |
| 1.5.3 | Experimental Procedures | 25 |
| 1.6 | Chloramine-T | 26 |
| 1.6.1 | Aminochalcogenation of Alkenes | 26 |
| 1.6.2 | Aminohydroxylation of Alkenes | 26 |
| 1.6.3 | Aziridination of Alkenes | 27 |
| 1.6.4 | Other Applications | 32 |
| 1.6.5 | Experimental Procedures | 34 |
| 1.7 | N-Sulfonyliminophenyliodinane | 35 |
| 1.7.1 | Transition Metal-Catalyzed Amination of Alkenes | 36 |
| 1.7.2 | Experimental Procedures | 37 |
| 1.8 | Transition Metal-Nitride Complexes | 38 |
| 1.8.1 | Nitrogen Atom Transfer Mediated by Transition Metal/Nitride Complexes | 38 |
| 1.8.2 | Experimental Procedures | 39 |
| 1.9 | Azido Derivatives | 41 |
| 1.9.1 | Electrophilic Amination of Organometallic Reagents with Organic Azides | 42 |
| 1.9.2 | Radical-Mediated Amination with Sulfonyl Azides | 43 |
| 1.9.3 | Hydroazidation of Alkenes with Sulfonyl Azides | 43 |
| 1.9.4 | Experimental Procedures | 44 |
| 1.10 | Gabriel-Type Reagents | 46 |
| 1.10.1 | Nucleophilic Amination Reactions | 46 |
| 1.10.2 | Experimental Procedure | 49 |
| 1.11 | Conclusion | 50 |
| 2 | Catalytic C-H Amination with Nitrenes
Philippe Dauban and Robert H. Dodd | 55 |
| 2.1 | Introduction | 55 |
| 2.2 | Historical Overview | 56 |
| 2.3 | Hypervalent Iodine-Mediated C-H Amination | 60 |
| 2.3.1 | Intramolecular C-H Amination | 60 |
| 2.3.1.1 | From NH2 Carbamates | 60 |
| 2.3.1.2 | From NH2 Sulfamates | 62 |
| 2.3.1.3 | From Other Nitrogen Functionalities | 65 |
| 2.3.2 | Intermolecular C-H Amination | 67 |
| 2.3.2.1 | General Scope and Limitations | 67 |
| 2.3.2.2 | Recent Major Improvements | 70 |
| 2.4 | Other Nitrene Precursors for C-H Amination | 73 |
| 2.4.1 | Azides | 73 |
| 2.4.2 | Haloamines | 74 |
| 2.4.3 | Carbamate Derivatives | 76 |
| 2.5 | Amination of Aromatic C-H Bonds | 77 |
| 2.6 | Applications in Total Synthesis | 80 |
| 2.6.1 | Application of Intramolecular C-H Amination with Carbamates | 80 |
| 2.6.2 | Application of Intramolecular C-H Amination with Sulfamates | 83 |
| 2.6.3 | Application of Intermolecular C-H Amination | 87 |
| 2.7 | Conclusions | 88 |
| 3 | Nitroalkenes as Amination Tools
Roberto Ballini, Enrico Marcantoni, and Marino Petrini | 93 |
| 3.1 | Introduction | 93 |
| 3.2 | General Strategies for the Synthesis of Nitroalkenes | 93 |
| 3.3 | Synthesis of Alkylamines | 95 |
| 3.3.1 | Monoamines | 95 |
| 3.3.2 | Amino Acid Derivatives | 98 |
| 3.3.3 | Amino Alcohols | 103 |
| 3.3.4 | Diamino Derivatives | 106 |
| 3.4 | Pyrrolidine Derivatives | 112 |
| 3.4.1 | Pyrrolidinones | 112 |
| 3.4.2 | Pyrrolidines | 115 |
| 3.5 | Piperidines and Piperazines | 124 |
| 3.6 | Pyrrolizidines and Related Derivatives | 126 |
| 3.7 | Arene-Fused Nitrogen Heterocycles | 132 |
| 3.7.1 | Pyrroloindole Derivatives | 132 |
| 3.7.2 | Carbolines and their Tryptamine Precursors | 132 |
| 3.7.3 | Arene-Fused Piperidine Compounds | 135 |
| 3.8 | Other Polycyclic Derivatives | 140 |
| 3.9 | Conclusion | 144 |
| 4 | Isocyanide-Based Multicomponent Reactions (IMCRs) as a Valuable Tool with which to Synthesize Nitrogen-Containing Compounds
Alexander Doemling | 149 |
| 4.1 | Introduction | 149 |
| 4.2 | The Ugi Reaction | 152 |
| 4.2.1 | Intramolecular Ugi Reactions Involving Two Functional Groups | 158 |
| 4.2.2 | The Ugi Reaction and Secondary Transformations | 166 |
| 4.3 | Passerini Reaction | 171 |
| 4.4 | van Leusen Reaction | 175 |
| 4.5 | Other IMCRs | 177 |
| 4.6 | Outlook | 180 |
| 5 | Direct Catalytic Asymmetric Mannich Reactions and Surroundings
Armando Córdova and Ramon Rios | 185 |
| 5.1 | Introduction | 185 |
| 5.2 | Organometallic Catalysts | 186 |
| 5.3 | Metal-Free Organocatalysis | 191 |
| 5.4 | Conclusions | 201 |
| 6 | Amino-Based Building Blocks for the Construction of Biomolecules
André Mann | 207 |
| 6.1 | Introduction | 207 |
| 6.2 | Propargylamines (PLAs) | 208 |
| 6.2.1 | Synthesis of PLAs | 209 |
| 6.2.2 | PLAs in Synthesis | 211 |
| 6.2.2.1 | PLAs in the Synthesis of Heterocycles | 211 |
| 6.2.2.2 | PLAs in Pd(0)-Catalyzed Processes | 211 |
| 6.2.2.3 | PLAs in Pericyclic Reactions | 213 |
| 6.2.2.4 | PLAs in Multicomponent Reactions (MCRs) | 215 |
| 6.2.2.5 | PLA in Radical Reactions | 217 |
| 6.3 | trans-4-Hydroxy-(S)-proline (HYP) | 217 |
| 6.3.1 | Structural Transformations of HYP | 218 |
| 6.3.1.1 | C-4 Alkylation of HYP | 218 |
| 6.3.1.2 | C-4 Fluorination and Fluoroalkylation of HYP | 218 |
| 6.3.1.3 | C-3 Functionalization of HYP | 221 |
| 6.3.2 | HYP in the Synthesis of Biomolecules | 221 |
| 6.3.2.1 | HYP in the Synthesis of Alkaloids | 221 |
| 6.3.2.2 | HYP in the Synthesis of Kainic Acid Derivatives | 222 |
| 6.3.2.3 | HYP in the Synthesis of Amino Sugars | 222 |
| 6.3.2.4 | Hepatitis C Inhibitors | 224 |
| 6.4 | L-Serine (SER) | 224 |
| 6.4.1 | SER and SER Derivatives in the Synthesis of Biomolecules | 225 |
| 6.4.1.1 | SER in the Synthesis of Carbolines | 225 |
| 6.4.1.2 | SER in the Synthesis of Furanomycin | 226 |
| 6.4.1.3 | SER in the Synthesis of Diketopiperazine Alkaloids | 226 |
| 6.4.1.4 | SER in the Synthesis of Cleomycin | 226 |
| 6.4.1.5 | SER in the Synthesis of Piperidine Alkaloids | 228 |
| 6.4.1.6 | SER in the Synthesis of Nonproteinogenic Amino Acids | 228 |
| 6.4.1.7 | SER in the Synthesis of  ,’-Diaminoacids | 229 |
| 6.4.1.8 | SER in the Synthesis of Rigidified Glutamic Acid | 230 |
| 6.5 | 4-Methoxypyridine (MOP) | 230 |
| 6.5.1 | MOP in the Synthesis of Biomolecules | 231 |
| 6.5.1.1 | MOP in the Synthesis of Alkaloids | 231 |
| 6.5.1.2 | MOP in the Synthesis of Plumerinine | 232 |
| 6.5.1.3 | MOP in the Synthesis of 2,4-Disubstituted Piperidines | 234 |
| 6.5.1.4 | MOP in the Synthesis of Toxins | 234 |
| 6.5.1.5 | MOP in the Synthesis of Tropanes | 235 |
| 6.6 | Aziridines (AZIs) | 236 |
| 6.6.1 | AZIs in the Synthesis of Biomolecules | 236 |
| 6.6.1.1 | AZIs in the Synthesis of 1,2-Diamines | 236 |
| 6.6.1.2 | AZIs in the Synthesis of -Amino Acids | 237 |
| 6.6.1.3 | AZI in the Synthesis of Ferruginine, an Acetylcholine Receptor | 238 |
| 6.6.1.4 | AZIs in the Synthesis of Tryptophan Derivatives | 238 |
| 6.6.1.5 | AZIs in the Synthesis of Functionalized Piperidines | 239 |
| 6.6.1.6 | An AZI in the Synthesis of the Alkaloid Pumiliotoxin | 240 |
| 6.6.1.7 | An AZI in the Synthesis of Phenylkainic Acid | 240 |
| 6.6.1.8 | AZIs in the Synthesis of Pseudodistomin Alkaloids | 241 |
| 6.7 | Homoallylamine (HAM) | 242 |
| 6.7.1 | Synthesis of HAMs | 242 |
| 6.7.2 | HAMs in the Synthesis of Biomolecules | 243 |
| 6.7.2.1 | HAM in the Synthesis of Imidazoazepines | 243 |
| 6.7.2.2 | HAMs in the Synthesis of Alkaloids | 244 |
| 6.7.2.3 | HAMs in the Synthesis of Piperidine Derivatives | 246 |
| 6.7.2.4 | HAMs in the Synthesis of Chiral Heterocycles | 247 |
| 6.8 | Indole (IND) | 247 |
| 6.8.1 | Synthesis of Indoles | 248 |
| 6.8.2 | INDs in the Synthesis of Biomolecules | 251 |
| 6.9 | Conclusion | 252 |
| 7 | Aminated Sugars, Synthesis, and Biological Activity
Francesco Nicotra, Barbara La Ferla, and Cristina Airoldi | 257 |
| 7.1 | Biological Relevance of Aminated Sugars | 257 |
| 7.1.1 | N-Acetylneuraminic Acid | 257 |
| 7.1.2 | Sialyl Lewis | X |
| 7.1.3 | Tumor-Associated Antigens | 259 |
| 7.1.4 | Chitin and Chitosan | 260 |
| 7.1.5 | Bacterial Polysaccharides | 260 |
| 7.1.6 | Glycosaminoglycans | 261 |
| 7.1.7 | Iminosugars | 262 |
| 7.1.8 | Sugar Amino Acids | 264 |
| 7.2 | Synthesis of Aminated Sugars | 266 |
| 7.2.1 | Amination at the Anomeric Center | 266 |
| 7.2.1.1 | Amination Exploiting Carbonyl Reactivity | 267 |
| 7.2.1.2 | Amination Exploiting Oxonium Ion Reactivity | 270 |
| 7.2.2 | Amination in the Sugar Chain | 273 |
| 7.2.2.1 | Amino Sugars by Nucleophilic Displacement | 273 |
| 7.2.2.2 | Amino Sugars through Intramolecular Displacements | 279 |
| 7.2.2.3 | Amino Sugars by Reductive Amination | 279 |
| 7.2.3 | Amination of Glycals | 283 |
| 7.2.4 | Amination through Ring-Opening of Epoxides | 287 |
| 7.3 | Synthesis of Iminosugars | 288 |
| 7.3.1 | Amination at the Anomeric center with Subsequent Cyclization | 290 |
| 7.3.1.1 | Exploitation of the Reactivity of the Carbonyl Function | 290 |
| 7.3.1.2 | Exploitation of the Reactivity of Lactones | 291 |
| 7.3.1.3 | Insertion of a New Electrophile | 292 |
| 7.3.2 | Amination at the Carbohydrate Chain and Subsequent Cyclization | 293 |
| 7.3.3 | Concomitant Insertion of Nitrogen at Both Carbon Atoms | 297 |
| 7.4 | Conclusions | 300 |
| 8 | Selective N-Derivatization of Aminoglycosides en Route to New Antibiotics and Antivirals
Floris Louis van Delft | 305 |
| 8.1 | Aminoglycoside Antibiotics | 305 |
| 8.2 | RNA Targeting by Aminoglycosides | 308 |
| 8.3 | The Role of Amino Functions in RNA Binding | 310 |
| 8.4 | Development of RNA-Targeting Drugs | 312 |
| 8.4.1 | Regioselective N-Modification of Naturally Occurring Aminoglycosides | 313 |
| 8.4.2 | Neamine-Based RNA ligands | 321 |
| 8.5 | Concluding Remarks | 327 |
| 9 | Evolution of Transition Metal-Catalyzed Amination Reactions: the Industrial Approach
Ulrich Scholz | 333 |
| 9.1 | Introduction: First Steps in the Field of Catalytic Aromatic Amination | 333 |
| 9.2 | Alternatives to Transition Metal-Catalyzed Arylamination | 335 |
| 9.2.1 | Reduction of Nitroarenes | 335 |
| 9.2.1.1 | Transfer Hydrogenation | 335 |
| 9.2.1.2 | Direct Hydrogenation | 336 |
| 9.2.1.3 | Other Methods for Nitro Reductions | 336 |
| 9.2.2 | Transition Metal-Free Alternatives for Amine–Halogen Exchange | 337 |
| 9.2.2.1 | Metal-Free Replacement of Halogens with Amines | 337 |
| 9.2.2.2 | The Chichibabin Reaction | 338 |
| 9.2.2.3 | The Nucleophilic Aromatic Substitution of Hydrogen (NASH Reaction) | 339 |
| 9.2.2.4 | Aromatic Amination by Use of Azides | 339 |
| 9.2.2.5 | The Minisci Reaction | 340 |
| 9.2.2.6 | The Bucherer Reaction | 340 |
| 9.2.2.7 | Metal-Free Replacement of Nitro Groups by Amines | 341 |
| 9.2.2.8 | Metal-Free Replacement of Sulfonic Acid Esters by Amines | 341 |
| 9.3 | The Quest for Industrial Applications of Transition Metal-Catalyzed Arylamination | 341 |
| 9.3.1 | Industrial-Scale Halogen–Amine Exchanges | 342 |
| 9.3.2 | Transition Metal-Catalyzed Direct Amination of Aromatic Compounds | 345 |
| 9.3.3 | Industrial-Scale Aminolysis of Phenols | 345 |
| 9.4 | Copper-Catalyzed Processes – More Recent Developments | 346 |
| 9.4.1 | Alternative Arylating Agents | 346 |
| 9.4.2 | Catalyst Tuning | 347 |
| 9.5 | Palladium-Catalyzed Processes | 353 |
| 9.5.1 | Early Developments | 353 |
| 9.5.2 | Ligand Developments | 355 |
| 9.5.3 | Other Components of the Reaction | 361 |
| 9.6 | Nickel-Catalyzed Processes | 361 |
| 9.7 | Summary | 363 |
| | Index | 377 |
