The Pauson-Khand reaction is an important reaction in the field of organic chemistry. It involves the transition-metal catalysed cycloaddition of an alkyne, an alkene and carbon monoxide, to produce cyclopentenones. The importance of this reaction originates from its high value in transforming simple components into the synthetically useful cyclopentenone unit, in which a high degree of molecular complexity can be achieved in a single step, with impressive stereochemical and regiochemical control.The Pauson-Khand Reaction investigates the nature and many variations of this reaction.Topics covered include: the mechanisms of Pauson?Khand-type reactionsnon chiral intramolecular and intermolecular versions of Pauson?Khand reactionsasymmetric Pauson?Khand reaction using chiral auxiliariesthe enantioselective Pauson?Khand reactionPauson?Khand reactions catalysed by metals other than cobaltunconventional Pauson?Khand reactionsthe Pauson?Khand reaction in total synthesisPresenting a comprehensive overview of this fundamental reaction, The Pauson-Khand Reaction will find a place on the bookshelves of any organic or organometallic chemist. INDICE: List of Contributors xiForeword xiiiPreface xv1. The Pauson-Khand Reaction - an Introduction 1William J. Kerr1.1 The Discovery and Early Evolution of the Khand Reaction 11.2 The Intermolecular Pauson-Khand Reaction 41.2.1 Regioselectivity of Alkyne Insertion 51.2.2 Regioselectivity of Alkene Insertion 61.3 The Intramolecular Pauson-Khand Reaction 81.4 Enhancing the Pauson-Khand Annulation by Reaction Promotion 91.4.1 Dry State Adsorption 91.4.2 Ultrasound Techniques 101.4.3 Microwave Promotion 101.4.4 Amine N-Oxide Additives 111.4.5 Sulfide Promoters 131.5 Catalytic Pauson-Khand Protocols 151.6 ConcludingRemarks 16Acknowledgements 17References 172. The Mechanism of the Pauson-Khand Reaction: Hypothesis, Experimental Facts, and Theoretical Investigations 23Xacobe C. Cambeiro and Miquel A. Peric'as2.1 Introduction 232.2 Stoichiometric Pauson-Khand Reaction 252.2.1 The Ligand Substitution Steps 252.2.2 Cobaltacycle Formation 292.2.3 CO Insertion 312.2.4 Reductive Elimination 322.3 Catalytic Pauson-Khand Reaction 322.4 Theoretical Studies 332.4.1 General Approach to the Mechanism 332.4.2 Regioselectivity. Early Steps of the Pauson-Khand Reaction 372.4.3 Stereoselectivity 412.5 Conclusions 46References 463. Non Chiral Pauson-Khand Reaction 49Takanori Shibata3.1 History of Co-Mediated Pauson-Khand Reaction 493.2 Mechanism of the Pauson-Khand Reaction 503.3 An Early Example of Catalytic Reaction 513.4 Catalytic Reactions by Aid of Additives 523.5 Catalytic Reaction Using in-situ Generated Low-Valent Cobalt Complex 553.6 Catalytic Reaction Using Multinuclear Cobalt Carbonyl Catalysts 593.7 Catalytic Reaction Using Heterogeneous Catalysts 613.8 Catalytic Reaction in Other Than Conventional Solvents 633.9 Intramolecular Reaction of Carbodiimides with Alkynes 65References 664. Diastereoselective Pauson-Khand Reaction using Chiral Pool Techniques (Chiral Substrates) 69Martin Kamlar, Jan Vesely, and Ramon Rios Torres4.1 Introduction and Background 694.2 Intramolecular Diastereoselective Pauson-Khand Reaction 704.3 Intermolecular Diastereoselective Pauson-Khand Reaction 874.4 Conclusion 90References 915. Asymmetric Intra- and Intermolecular Pauson-Khand Reactions: The Chiral Auxiliary Approach 95Albert Moyano5.1 Introduction 965.2 Asymmetric Intramolecular PKRs with the Aid of Chiral Auxiliaries 995.2.1 Chiral Alkoxyacetylenes 995.2.2 Chiral Acetylene Thioethers 1045.2.3 Chiral 2-alkynoate Derivatives 1065.2.4 Chiral O-alkyl Enol Ethers 1085.2.5 Alkenylsulfoxides 1135.2.6 Asymmetric Intramolecular PKRs Mediated by Chiral Auxiliaries Located in the Enyne Tether 1145.3 Asymmetric Intermolecular PKRs with the Aid of Chiral Auxiliaries 1165.3.1 Chiral Alkoxyacetylenes 1165.3.2 Chiral Acetylene Thioethers 1245.3.3 Alkynyl Sulfoxides 1255.3.4 Chiral Ynamines and Ynamides 1265.3.5 Chiral 2-alkynoates 1285.3.6 Alkenyl Sulfoxides 1355.4 ChiralReagents for the Kinetic Resolution of PK Cycloadducts 1385.5 Conclusion 140Acknowledgements 140References 1406. The Enantioselective Pauson-Khand Reaction147Agust´? Lled´o, Xavier Verdaguer and Antoni Riera6.1 Introduction 1486.2 Mechanistic Considerations. Topology of Alkyne-Dicobalt Clusters 1486.3 Intrinsically Chiral Dicobalt Clusters 1506.3.1 Resolution of Monophosphine Complexes1506.3.2 Synthesis of Chiral Monophosphine Complexes Using Chiral N-Oxides 1516.3.3 Heterobimetallic Complexes 1516.4 Chiral Promoters 1536.4.1 Sulfoxides 1536.4.2 Chiral N-Oxides 1536.5 Chiral Ligands 1556.5.1 Sulfides 1556.5.2 Cyclopentadienes (Heterobimetallic) 1566.5.3 C-Chiral and Axially Chiral Phosphines 1566.5.4 C2-Symmetric Bridging Bis-phosphines 1616.5.5 C-Chiral Bidentate (P,S) Ligands 1626.5.6 S-Chiral Bidentate (P,S) Ligands 1676.6 Synthetic Applications 1716.7 Conclusion 176References 1767. Recent Advancement of Catalytic Pauson-Khand-type Reactions 181Fuk Loi Lam, Hang Wai Lee, Jun Wang and Fuk Yee Kwong7.1 Introduction 1817.2 Rhodium-Catalyzed Pauson-Khand-Type Cyclizations 1827.3 Iridium-Catalyzed Pauson-Khand-Type Cyclizations 1947.4 Titanium-Catalyzed Pauson-Khand-Type Cyclizations 1987.5 Ruthenium-Catalyzed Pauson-Khand-TypeCyclizations 2007.6 Nickel- and Palladium-Catalyzed Pauson-Khand-Type Cyclizations 2017.7 Tandem Reactions and Miscellaneous (other than Co complex) 2047.8Conclusion 206Acknowledgements 206References 2068. Recent Adventures with thePauson-Khand Reaction in Total Synthesis 211Scott G. Van Ornum, Sarah Hoernerand James M. Cook8.1 Introduction 2128.2 (+)-Epoxydictymene 2128.3 (±)-Pentalenene and (-)-Pentalenene 2148.4 The Tandem Pauson-Khand Reaction Directed Towards the Synthesis of Dicyclopentapentalenes 2158.5 Enantioselective Total Synthesis of (-)--Kainic Acid 2198.6 The Total Synthesis of Paecilomycine A 2208.7 The Total Synthesis of (+)-Achalensolide 2218.8 The Total Synthesis of (-)-Alstonerine 2228.9 The Total Synthesis of (±)-8-Hydroxystreptazolone 2248.10 The Formal Total Synthesis of (±)-- and -Cedrene 2268.11 Additional Applicationsof the Pauson-Khand Reaction in Total Synthesis 2278.12 Conclusions 230Acknowledgements 231References 2319. Heterogeneous Catalytic Pauson-Khand Reaction 239Young Keun Chung9.1 Introduction 2409.2 Development of Heterogeneous Catalysts for PKR 2409.2.1 Polymer-Supported Catalytic Systems 2419.2.2 Bulk Cobalt as a Catalyst 2429.2.3 Raney Cobalt 2439.2.4 Mesoporous Organized Zirconium Oxide Silica Powders as Catalyst 2449.2.5 Mesoporous Graphitic Carbon as a Promoter 2459.3 Transition Metal Nanoparticle Catalyst 2469.3.1 Colloidal Cobalt Nanoparticles 2479.3.2 Cobalt Nanoparticles on Charcoal 2479.3.3 Poly(ethylene glycol)-Stabilized Cobalt Nanoparticles 2499.4 Bimetallic Nanoparticle Catalysts2509.4.1 Immobilized Heterobimetallic Ru/Co Nanoparticle 2509.4.2 Heterobimetallic Co/Rh Nanoparticles 2519.5 Sequential Action of Two Different Catalysts in One-Pot Reactions 2619.5.1 Chiral Pd(II) Complex and Bulk Cobalt on Charcoal-Catalyzed Tandem Asymmetric Allylic Alkylation and PK Annulation Reactions 2629.5.2 Pd(II) Complex and Cobalt Nanoparticle-Catalyzed Three-Step One-Pot Synthesis of Fenestranes 2629.5.3 Palladium and Cobalt Nanoparticles-Catalyzed Tandem Allylic Alkylation and PKRs 2649.6 Conclusion 265References 26610. OtherTransition Metal-Mediated Cyclizations Leading to Cyclopentenones 275Ramon Rios Torres and Jan Vesely10.1 Introduction and Background 27610.2 [4+1] Strategies for the Synthesis of Cyclopentenones 27810.3 [3+2] Strategies for the Synthesis of Cyclopentenones 28310.3.1 Iron Promoted Reactions 28310.3.2 Synthesisof Cyclopentenones via [3+2] Cycloadditions of Fisher Alkenyl Complexes 28410.4 Nickel(0) and Palladium(0) Synthesis of Cyclopentenones 28510.5 Metal Carbine Strategies for the Synthesis of Cyclopentenones 28910.5.1 Cyclopropylcarbene Chromium Complexes 28910.5.2 Rhodium(II)-Catalyzed Strategies 29110.6 Other Methodologies 29210.7 Conclusions 298Experimental 299References and Notes 299Index 307
- ISBN: 978-0-470-97076-8
- Editorial: John Wiley & Sons
- Encuadernacion: Cartoné
- Páginas: 336
- Fecha Publicación: 20/04/2012
- Nº Volúmenes: 1
- Idioma: Inglés