Practical Synthetic Organic Chemistry

Diese Publikation ist ein Praktikerbuch für Organiker. Der Schwerpunkt liegt auf den Reaktionen, die am verlässlichsten und nützlichsten sind. Die Autoren der einzelnen Kapitel stellen Chemiker die Informationen zur Verfügung, die für die strategische Planung einer Synthese und Wiederholung der Verfahren im Labor notwendig sind.

• Fasst alle wesentlichen Entwicklungen und Konzepte in einer Publikation zusammen und deckt die meisten der wichtigen Reaktionen in der organischen Chemie ab, u. a. Substitutions-, Additions-, Eliminierungsreaktionen, Umlagerung, Oxidation, Reduktion.
• Behandelt die wichtigsten Reaktionen ausführlicher und zeigt die grundlegenden Prinzipien, Vor- und Nachteile der Methoden, Mechanismen und Techniken, um Reaktionen im Labor erfolgreich durchzuführen.
• Mit neuen Inhalten zu den jüngsten Fortschritten in den Bereichen CH-Aktivierung, Photoredox-Katalyse und Elektrochemie, kontinuierliche chemische Prozesse und Anwendung der Biokatalyse in der Synthese.
• Bietet überarbeitete Kapitel mit neuen und zusätzlichen chemischen Beispielen aus der Praxis.

Auteur

Stéphane Caron is an Executive Director in Chemical Research & Development at Pfizer Inc.

Contenu

List of Contributors xxxi Preface xxxiii 1 Aliphatic Nucleophilic Substitution 1 Jade D. Nelson 1.1 Introduction 1 1.2 Oxygen Nucleophiles 1 1.3 Phosphorus Nucleophiles 21 1.4 Sulfur Nucleophiles 21 1.5 Nitrogen Nucleophiles 26 1.6 Halogen Nucleophiles 38 1.7 Carbon Nucleophiles 47 1.8 Nucleophilic Substitution at a Sulfonyl Sulfur Atom 60 2 Addition to Carbon-Heteroatom Multiple Bonds 65 Prantik Maity and Rajappa Vaidyanathan 2.1 Introduction 66 2.2 Addition of Water to Aldehydes and Ketones: Formation of Hydrates 66 2.3 Addition of Bisulfite to Aldehydes and Ketones 67 2.4 The Addition of Alcohols to Aldehydes and Ketones: Acetal Formation 69 2.5 The Addition of Thiols to Aldehydes and Ketones: S,S-Acetal Formation 71 2.6 Reductive Etherification 72 2.7 Addition of NH3, RNH2, and R2NH 74 2.8 Formation of Hydrazones 79 2.9 Formation of Oximes 80 2.10 The Formation of gem-Dihalides from Aldehydes and Ketones 80 2.11 The Aldol Reaction 82 2.12 Allylorganometallics: Stannane, Borane, and Silane 92 2.13 The Nozaki-Hiyama-Kishi Reaction 97 2.14 Addition of Transition Metal Alkynylides to Carbonyl Compounds 99 2.15 Addition of Organometallic Reagents to Carbonyls 100 2.17 The Reformatsky Reaction 104 2.18 The Wittig Reaction 106 2.19 Horner-Wadsworth-Emmons Reaction 108 2.20 Peterson Olefination 109 2.21 Julia-Lythgoe Olefination 110 2.22 Tebbe Methylenation 112 2.23 The Mannich Reaction 113 2.24 The Strecker Reaction 115 2.25 Hydrolysis of Carbon-Nitrogen Double Bonds 117 2.26 Conversion of Carboxylic Acids to Acyl Chlorides 118 2.27 Synthesis of Acyl Fluorides from Carboxylic Acids 122 2.28 Formation of Amides from Carboxylic Acids 123 2.29 Formation of Amides from Esters 130 2.30 Hydrolysis of Acyl Halides 132 2.31 Conversion of Carboxylic Acids to Esters 132 2.32 Hydrolysis of Amides 136 2.33 Conversion of N-Acyloxazolidinones to Other Carboxyl Derivatives 139 2.34 Alcoholysis of Amides 140 2.35 Hydrolysis of Esters 141 2.36 Transesterification 143 2.37 Alkyl Thiol Addition to Esters 144 2.38 Addition of Organometallic Reagents to Carboxylic Acid Derivatives 145 2.39 The Kulinkovich Cyclopropanation 149 2.40 Synthesis of Acyl Cyanides 150 2.41 The Ritter Reaction 151 2.42 Thorpe Reaction 154 2.43 Addition of Organometallic Reagents to Nitriles 155 2.44 Conversion of Nitriles to Amides, Esters, and Carboxylic Acids 155 2.45 Conversion of Nitriles to Thioamides 158 2.46 The Addition of Ammonia or Amines to Nitriles 160 2.47 The Addition of Alcohol to Nitriles 161 2.48 Alkyl Thiol Addition to Nitriles 162 2.49 The Blaise Reaction 162 2.50 The Addition of Alcohols to Isocyanates 163 2.51 The Addition of Amines and Amides to Isocyanates 164 2.52 The Formation of Xanthates 165 2.53 The Addition of Amines to Carbon Dioxide 166 2.54 The Addition of Amines to Carbon Disulfide 167 2.55 Addition of Organometallic Reagents to Carbon Dioxide 167 3 Addition to Carbon-Carbon Multiple Bonds 169 John A. Ragan 3.1 Introduction 169 3.2 Hydrogen-Halogen Addition (Hydrohalogenation) 169 3.3 Hydrogen-Oxygen Addition 173 3.4 Hydrogen-Nitrogen Addition (Hydroamination) 178 3.5 Hydrogen-Carbon Addition (Hydroalkylation) 180 3.6 Halogen-Halogen Addition 191 3.7 Hydroxy-Halogen Addition 192 3.8 Amino-Halogen Addition 194 3.9 Carbon-Halogen Addition 194 3.10 Oxygen-Oxygen Addition 196 3.11 Oxygen-Nitrogen Addition 202 3.12 Nitrogen-Nitrogen Addition 204 3.13 Carbon-Oxygen Addition 206 3.14 Carbon-Nitrogen Addition 211 3.15 Carbon-Carbon Addition 212 4 Nucleophilic Aromatic Substitution 231 Stéphane Caron and Emma McInturff 4.1 Introduction 231 4.2 Oxygen Nucleophiles 232 4.3 Sulfur Nucleophiles 234 4.4 Nitrogen Nucleophiles 236 4.5 Halogen Nucleophiles 241 4.6 Carbon Nucleophiles 243 4.7 ortho-Arynes 245 5 Electrophilic Aromatic Substitution 247 Stéphane Caron and Emma McInturff 5.1 Introduction 247 5.2 Nitrogen Electrophiles 247 5.3 Sulfur Electrophiles 250 5.4 Halogenation 253 5.5 Carbon Electrophiles 257 6 Selected Catalytic Reactions 269 Sebastien Monfette, Adam R. Brown, Pascal Dubé, Nathan D. Ide, Chad A. Lewis, Jared L. Piper, Shashank Shekhar, and Shu Yu 6.1 Introduction 269 6.2 Organoboron Reagents:The Suzuki-Miyaura Coupling 270 6.3 Organomagnesium Reagents: Kumada-Corriu Coupling 282 6.4 Organozinc Reagents: Negishi Coupling 287 6.5 Cross-Electrophile Coupling 291 6.6 Organotin Reagents: The Stille Coupling (Migita-Stille Reaction) 292 6.7 Cross-Coupling Reactions with Organosilicon Compounds 295 6.8 Metal-catalyzed Coupling of Alkynes (Sonogashira Coupling) 296 6.9 Metal-Catalyzed Coupling of Alkenes (Heck Coupling) 298 6.10 Enolate Arylations 303 6.11 Pd- and Cu-Catalyzed Aryl C--N Bond Formation 306 6.12 Pd- and Cu-Catalyzed Aryl C--O Bond Formation 320 6.13 Pd- and Cu-Catalyzed Aryl C--S Bond Formation 322 6.14 Aryl C--B Bond Formation 324 6.15 Pd-Catalyzed Aryl C--CN Bond Formation 327 6.16 Metal-Catalyzed Allylic Substitution 329 6.17 Catalytic Metal-Mediated Methods for Fluorination 337 6.18 Selected Metal-Mediated C--H Functionalization 347 6.19 C--X Bond Forming Reactions via Borrowed Hydrogen Methodologies 357 6.20 Alkene and Alkyne Metathesis Reactions 362 6.21 Organocatalysis 369 7 Rearrangements 377 David H. Brown Ripin and Chad A. Lewis 7.1 Introduction 377 7.2 [1,2]-Rearrangements 377 Other Rearrangements 402 7.3 Other Rearrangements 402 7.4 Miscellaneous Migrations 420 8 Eliminations 425 Sally Gut Ruggeri 8.1 Introduction 425 8.2 Formation of Alkenes 425 8.3 Formation of Dienes 438 8.4 Formation of Alkynes 442 8.5 Formation of C=N bonds 444 8.6 Formation of Nitriles 445 8.7 Formation of Ketenes and Related Compounds 447 8.8 Fragmentations 449 8.9 Dehydrating Reagents 451 9 Reductions 455 Sally Gut Ruggeri, Stéphane Caron, Pascal Dubé, Nathan D. Ide, Kristin E. Price Wiglesworth, John A. Ragan, and Shu Yu 9.1 Introduction 455 9.2 Reduction of C--C Bonds 455 9.3 Reduction of C--N Bonds 471 9.4 Reduction of C--O Bonds 479 9.5 Reduction of C--S Bonds 494 9.6 Reduction of C--X Bonds 500 9.7 Reduction of Heteroatom-Heteroatom Bonds 504 10 Oxidations 513 Eric C. Hansen, Robert Perkins, and David H. Brown Ripin 10.1 Introduction 513 10.2 Oxidation of C--C Single and Double Bonds 514 10.3 Oxidation of C--H Bonds 520 10.4 Oxidation of Carbon-Oxygen Bonds and at Carbon Bearing an Oxygen Substituent 536 10.5 Oxidation of Aldehydes to Carboxylic Acids and Derivatives 543 10.6 Oxidation of Carbon-Nitrogen Bonds and at Carbon Bearing a Nitrogen Substituent 546 10.7 Oxidation of Nitrogen Functionalities 548 10.8 Oxidation of Sulfur and at Carbon Adjacent to Sulfur 555 10.9 Oxidation of Other Functionality 561 11 Selected Free Radical Reactions 563 Christophe Allais, Eric C. Hansen, Nathan D. Ide, Robert J. Perkins, and Elizabeth C. Swift 11.1 Introduc…