Transition metals open up new opportunities for synthesis, because their means of bonding and their reaction mechanisms differ from those of the elements of the s and p blocks. In the last two decades the subject has mushroomed - established reactions are seeing both technical improvements and increasing numbers of applications, and new reactions are being developed. The practicality ofthe subject is demonstrated by the large number of publications coming from the process development laboratories of pharmaceutical companies, and its importance is underlined by the fact that three Nobel prizes have been awarded for discoveries in this field in the 21st Century already.Organic Synthesis Using Transition Metals, 2nd Edition considers the ways in which transition metals, as catalysts and reagents, can be used in organic synthesis, both for pharmaceutical compounds and for natural products. It concentrates on the bond-formingreactions that set transition metal chemistry apart from "classical" organic chemistry. Each chapter is extensively referenced and provides a convenient point of entry to the research literature. Topics covered include:introduction to transition metals in organic synthesiscoupling reactionsC-H activationcarbonylative coupling reactionsalkene and alkyne insertion reactionselectrophilic alkene and alkyne complexesreactions of alkyne complexescarbene complexesh3- orp-allyl -allyl complexesdiene, dienyl and arene complexescycloaddition and cycloisomerisation reactionsFor this second edition the text has been extensively revised and expanded to reflect the significant improvements and advances inthe field since the first edition, as well as the large number of new transition metal-catalysed processes that have come to prominence in the last 10 years – for example the extraordinary progress in coupling reactions using “designer” ligands, catalysis using gold complexes, new opportunities arising from metathesis chemistry, and C-H activation – without neglecting the well established chemistry of metals such as palladium.Organic Synthesis Using Transition Metals, 2nd Edition will find a place on the bookshelvesof advanced undergraduates and postgraduates working in organic synthesis, catalysis, medicinal chemistry and drug discovery. It is also useful for practising researchers who want to refresh and enhance their knowledge of the field. INDICE: 1 Introduction 11.1 The Basics 21.2 The Basic Structural Types 21.2.1 Phosphines 51.2.2 Phosphites 81.2.3 N-Heterocyclic Carbenes 91.2.4 Other Ligands 101.2.5 Quantifying Ligand Effects 101.2.6 Heterogeneous Catalysis 101.3 Just how many Ligands Can Fit around a Metal Atom? 101.4 Method 1: Covalent 111.5 Method 2: Ionic 121.5.1 Examples 131.6 Mechanism and the Basic Reaction Steps 131.6.1 Coordination and Dissociation 141.6.2 Oxidative Addition and Reductive Elimination 151.6.3 Transmetallation 151.6.4 Alkene and Alkyne Insertion 151.6.5 CO insertion 161.6.6 -Hydride Elimination 161.6.7 Oxidative Cyclization 171.7 Catalysis 18References 192 Coupling Reactions 212.1 Carbon-Carbon Bond Formation 212.1.1 The Main-Group Metal, M 222.1.2 Limitation 232.1.3 Reactivity of the Leaving Group 232.1.4 Selectivity 252.2 Lithium and Magnesium: Kumada Coupling 272.3 Zinc: the Negishi Reaction 322.4 Aluminium and Zirconium 352.5 Tin: the Stille Reaction 372.5.1 Vinyl Stannanes 412.5.2 Aryl and Heteroaryl Stannanes 422.5.3 The Intramolecular Stille Reaction 422.5.4 Coupling of Acid Chlorides 422.5.5 Stille Coupling of Triflates 442.5.6 Stille Coupling of Alkyl Halides 442.5.7 Stille Reaction Troubleshooting 442.6 Boron: the Suzuki Reaction 462.6.1 Alkenyl Borane Coupling Reactions 482.6.2 Alkyl Borane Coupling Reactions 502.6.3 Aryl Borane Coupling Reactions 522.6.4 Suzuki Coupling of Alkyl Halides 562.7 Silicon: the Hiyama Reaction 572.8 Copper: the SonogashiraReaction 612.9 Other Metals 672.10 Homocoupling 672.11 Enolate and Phenoxide Coupling 692.12 Heteroatom Coupling 702.12.1 Palladium-Catalysed Synthesis of Amine Derivatives 722.12.2 Palladium-Catalysed Synthesis of Ethers 762.12.3 Ullmann Coupling 782.12.4 Formation of Other C-X bonds 81References 823 C-H Activation 893.1 Arenes and Heteroarenes 913.1.1 Fujiwara-Heck Reaction 913.1.2 Biaryl Coupling 933.2 Aldehydes 1003.3 Borylation and Silylation 1023.4 Allylic Functionalization 1033.5 Unfunctionalized C-H Bonds 1053.5.1 Carbon-HeteroatomBond Formation 1053.5.2 Carbon-Carbon Bond Formation 109References 1154 Carbonylation 1174.1 Carbonylative Coupling Reactions: Synthesis of Carbonyl Derivatives 1174.2 Carbonylative Coupling Reactions: Synthesis of Carboxylic Acid Derivatives 1224.3 Carbonylation of Alkenes and Alkynes 1274.3.1 The Carbonylative Heck Reaction 1274.3.2 Other Carbonylation Reactions of Allenes and Alkynes1294.4 Hydroformylation 1304.4.1 Directed Hydroformylation 1354.4.2 Asymmetric Hydroformylation 1384.5 Stoichiometric Carbonylation using Carbonyl Complexes 1394.5.1 Iron and Cobalt Carbonyl Anions 1394.5.2 Ferrilactones and Ferrilactams 1424.5.3 Molybdenum and Tungsten Carbonyls 1454.6 Carboxylation 1464.7 Decarbonylation and Decarboxylation 148References 1505 Alkene and Alkyne Insertion Reactions 1535.1 The Heck Reaction 1535.1.1 The Organic Halide 1535.1.2 Leaving Groups 1555.1.3 Catalysts, Ligands and Reagents 1585.1.4 The Alkene: Scope and Reactivity 1595.1.5 The Alkene: Regio- and Stereoselectivity 1605.1.6 Cyclic Alkenes 1615.1.7 Isomerization 1625.1.8 The Intramolecular Heck Reaction 1635.1.9 The Asymmetric Heck Reaction 1645.1.10 Tandem Reactions 1695.1.11 Heck-Like Reactions of Organometallics 1745.2 Insertion Reactions Involving Zirconium and Titanium 1755.2.1 Hydrozirconation and Carbozirconation 1755.2.2 Alkene and Alkyne Complexes 1775.2.3 Zirconium-Mediated Carbomagnesiation 1825.2.4The Kulinkovich Reaction 185References 1886 Electrophilic Alkene and Alkyne Complexes 1916.1 Electrophilic Palladium Complexes 1916.1.1 Tandem Reactions Involving CO or Alkene Insertion 1986.1.2 Tandem Reactions with Oxidative Addition 2076.2 Other Metals: Silver, Gold, Platinum and Rare Earths 2106.2.1 Reactions of Alkenes 2106.2.2 Reactions of Allenes 2136.2.3 Reactions of Alkynes 2166.2.4 The Hashmi Phenol Synthesis 2236.2.5 Ene-Yne Cyclization 2256.3 Iron 2296.3.1 Fp Complexes of Alkenes 2296.3.2 Fp Complexes of Alkynes 2346.3.3 Alkylation of Allyl Fp Complexes and Formal Cycloadditions 2346.4 Cobaloxime -Cations 235References 2377 Reactions of Alkyne Complexes 2417.1 Alkyne Cobalt Complexes 2417.2 Propargyl Cations: The Nicholas Reaction 2447.3 The Pauson-Khand Reaction 2467.3.1 Asymmetric Pauson-Khand Reaction 2487.3.2 The Hetero-Pauson-Khand Reaction 2497.4 Synthesis Using Multiple Cobalt Reactions 250References 2518 Carbene Complexes 2538.1 Fisher Carbenes 2538.1.1 Demetallation 2588.1.2 The D¨otz Reaction 2588.1.3 Not the Dotz Reaction 2638.1.4 Fischer Carbene Photochemistry 2678.2 Vinylidene Complexes 2698.3 Metathesis Reactions Involving Carbene Complexes 2738.3.1 Tebbe€™s Reagent 2748.3.2 Alkene (Olefin) Metathesis 2788.3.3 Ring-Closing Metathesis 2798.3.4 Cross-Metathesis 2918.3.5 Ring-Opening Metathesis 2968.3.6 Asymmetric Metathesis 2978.3.7 Ene-Yne Metathesis 3008.3.8 Ene-Yne-Ene Metathesis 3038.3.9 Tandem Reactions 3068.3.10 Metathesis SideReactions 3068.4 Carbyne Complexes 3108.4.1 Alkyne Metathesis 3108.5 Carbene Complexes from Diazo Compounds 3128.5.1 Nucleophilic Trapping 3138.5.2 C-H Insertion Reactions of Carbene Complexes 3158.5.3 C-H Insertion Reactions of Nitrene Complexes 316References 3199 3- or -Allyl Complexes 3259.1 Stoichiometric Reactions of -Allyl Complexes 3259.2 Catalysis: Mostly Palladium 3289.2.1 Regioselectivity 3319.2.2 Internal versus Terminal Attack 3339.2.3 Stereoselectivity 3359.2.4 Asymmetric Allylation 3379.2.5 Synthesis Using Palladium Allyl Chemistry 3409.2.6 Base-Free Allylation 3439.2.7 Allylation with Decarboxylation 3479.2.8 Allyl as a Protecting Group 3509.2.9 Other Routes to 3- or -Allyl Palladium Complexes 3529.3 Propargyl Compounds 357References 35710 Diene, Dienyl and Arene Complexes 36110.1 4-Diene Complexes 36110.1.1 Electrophilic Attack 36410.1.2 Nucleophilic Attack 36610.1.3 Deprotonation 37010.2 5-Dienyl Complexes 37110.2.1 Nucleophilic Attack 37210.3 6-Arene Complexes 37710.3.1 Nucleophilic Attack 38010.3.2 Deprotonation 38510.4 2-Arene Complexes 387References 38911 Cycloaddition and Cycloisomerization Reactions 39111.1 Formal Six-Electron, Six-Atom Cycloadditions 39111.1.1 The [4 + 2] Cycloaddition 39111.1.2 The [2 +2 + 2] Cycloaddition 39411.2 Cycloadditions Involving Fewer than Six Atoms 40211.2.1 Four-Membered Rings 40211.2.2 Five-Membered Rings through TMM Methods 40211.2.3 Other Five-Membered Ring Formations 40511.3 Cycloadditions InvolvingMore than Six Atoms 40711.3.1 The [5 + 2] Cycloaddition 40711.3.2 The [4 + 4]Cycloaddition 41011.3.3 The [6 + 2] and [6 + 4] Cycloadditions 41111.4 Isomerization 41411.5 Cycloisomerization and Related Reactions 415References 426Abbreviations 431Index 433
- ISBN: 978-1-119-94286-3
- Editorial: John Wiley & Sons
- Encuadernacion: Rústica
- Páginas: 464
- Fecha Publicación: 10/04/2012
- Nº Volúmenes: 1
- Idioma: Inglés