The Pauson-Khand Reaction -- Contents -- List of Contributors -- Foreword -- Preface -- 1. The Pauson-Khand Reaction - an Introduction -- 1.1 The Discovery and Early Evolution of the Khand Reaction -- 1.2 The Intermolecular Pauson-Khand Reaction -- 1.2.1 Regioselectivity of Alkyne Insertion -- 1.2.2 Regioselectivity of Alkene Insertion -- 1.3 The Intramolecular Pauson-Khand Reaction -- 1.4 Enhancing the Pauson-Khand Annulation by Reaction Promotion -- 1.4.1 Dry State Adsorption -- 1.4.2 Ultrasound Techniques -- 1.4.3 Microwave Promotion -- 1.4.4 Amine N-Oxide Additives -- 1.4.5 Sulfide Promoters -- 1.5 Catalytic Pauson-Khand Protocols -- 1.6 Concluding Remarks -- Acknowledgements -- References -- 2. The Mechanism of the Pauson-Khand Reaction: Hypothesis, Experimental Facts, and Theoretical Investigations -- 2.1 Introduction -- 2.2 Stoichiometric Pauson-Khand Reaction -- 2.2.1 The Ligand Substitution Steps -- 2.2.2 Cobaltacycle Formation -- 2.2.3 CO Insertion -- 2.2.4 Reductive Elimination -- 2.3 Catalytic Pauson-Khand Reaction -- 2.4 Theoretical Studies -- 2.4.1 General Approach to the Mechanism -- 2.4.2 Regioselectivity. Early Steps of the Pauson-Khand Reaction -- 2.4.3 Stereoselectivity -- 2.5 Conclusions -- References -- 3. Non Chiral Pauson-Khand Reaction -- 3.1 History of Co-Mediated Pauson-Khand Reaction -- 3.2 Mechanism of the Pauson-Khand Reaction -- 3.3 An Early Example of Catalytic Reaction -- 3.4 Catalytic Reactions by Aid of Additives -- 3.5 Catalytic Reaction Using in-situ Generated Low-Valent Cobalt Complex -- 3.6 Catalytic Reaction Using Multinuclear Cobalt Carbonyl Catalysts -- 3.7 Catalytic Reaction Using Heterogeneous Catalysts -- 3.8 Catalytic Reaction in Other Than Conventional Solvents -- 3.9 Intramolecular Reaction of Carbodiimides with Alkynes -- References.

4. Diastereoselective Pauson-Khand Reaction using Chiral Pool Techniques (Chiral Substrates) -- 4.1 Introduction and Background -- 4.2 Intramolecular Diastereoselective Pauson-Khand Reaction -- 4.3 Intermolecular Diastereoselective Pauson-Khand Reaction -- 4.4 Conclusion -- References -- 5. Asymmetric Intra- and Intermolecular Pauson-Khand Reactions: The Chiral Auxiliary Approach -- 5.1 Introduction -- 5.2 Asymmetric Intramolecular PKRs with the Aid of Chiral Auxiliaries -- 5.2.1 Chiral Alkoxyacetylenes -- 5.2.2 Chiral Acetylene Thioethers -- 5.2.3 Chiral 2-alkynoate Derivatives -- 5.2.4 Chiral O-alkyl Enol Ethers -- 5.2.5 Alkenyl sulfoxides -- 5.2.6 Asymmetric Intramolecular PKRs Mediated by Chiral Auxiliaries Located in the Enyne Tether -- 5.3 Asymmetric Intermolecular PKRs with the Aid of Chiral Auxiliaries -- 5.3.1 Chiral Alkoxyacetylenes -- 5.3.2 Chiral Acetylene Thioethers -- 5.3.3 Alkynyl Sulfoxides -- 5.3.4 Chiral Ynamines and Ynamides -- 5.3.5 Chiral 2-alkynoates -- 5.3.6 Alkenyl Sulfoxides -- 5.4 Chiral Reagents for the Kinetic Resolution of PK Cycloadducts -- 5.5 Conclusion -- Acknowledgements -- References -- 6. The Enantioselective Pauson-Khand Reaction -- 6.1 Introduction -- 6.2 Mechanistic Considerations. Topology of Alkyne-Dicobalt Clusters -- 6.3 Intrinsically Chiral Dicobalt Clusters -- 6.3.1 Resolution of Monophosphine Complexes -- 6.3.2 Synthesis of Chiral Monophosphine Complexes Using Chiral N-Oxides -- 6.3.3 Heterobimetallic Complexes -- 6.4 Chiral Promoters -- 6.4.1 Sulfoxides -- 6.4.2 Chiral N-Oxides -- 6.5 Chiral Ligands -- 6.5.1 Sulfides -- 6.5.2 Cyclopentadienes (Heterobimetallic) -- 6.5.3 C-Chiral and Axially Chiral Phosphines -- 6.5.4 C2-Symmetric Bridging Bis-phosphines -- 6.5.5 C-Chiral Bidentate (P,S) Ligands -- 6.5.6 S-Chiral Bidentate (P,S) Ligands -- 6.6 Synthetic Applications -- 6.7 Conclusion -- References.

7. Recent Advancement of Catalytic Pauson-Khand-type Reactions -- 7.1 Introduction -- 7.2 Rhodium-Catalyzed Pauson-Khand-Type Cyclizations -- 7.3 Iridium-Catalyzed Pauson-Khand-Type Cyclizations -- 7.4 Titanium-Catalyzed Pauson-Khand-Type Cyclizations -- 7.5 Ruthenium-Catalyzed Pauson-Khand-Type Cyclizations -- 7.6 Nickel- and Palladium-Catalyzed Pauson-Khand-Type Cyclizations -- 7.7 Tandem Reactions and Miscellaneous (other than Co complex) -- 7.8 Conclusion -- Acknowledgements -- References -- 8. Recent Adventures with the Pauson-Khand Reaction in Total Synthesis -- 8.1 Introduction -- 8.2 (+)-Epoxydictymene -- 8.3 (±)-Pentalenene and (-)-Pentalenene -- 8.4 The Tandem Pauson-Khand Reaction Directed Towards the Synthesis of Dicyclopentapentalenes -- 8.5 Enantioselective Total Synthesis of (-)-α-Kainic Acid -- 8.6 The Total Synthesis of Paecilomycine A -- 8.7 The Total Synthesis of (+)-Achalensolide -- 8.8 The Total Synthesis of (-)-Alstonerine -- 8.9 The Total Synthesis of (±)-8α-Hydroxystreptazolone -- 8.10 The Formal Total Synthesis of (±)-α- and β-Cedrene -- 8.11 Additional Applications of the Pauson-Khand Reaction in Total Synthesis -- 8.12 Conclusions -- Acknowledgements -- References -- 9. Heterogeneous Catalytic Pauson-Khand Reaction -- 9.1 Introduction -- 9.2 Development of Heterogeneous Catalysts for PKR -- 9.2.1 Polymer-Supported Catalytic Systems -- 9.2.2 Bulk Cobalt as a Catalyst -- 9.2.3 Raney Cobalt -- 9.2.4 Mesoporous Organized Zirconium Oxide Silica Powders as Catalyst -- 9.2.5 Mesoporous Graphitic Carbon as a Promoter -- 9.3 Transition Metal Nanoparticle Catalyst -- 9.3.1 Colloidal Cobalt Nanoparticles -- 9.3.2 Cobalt Nanoparticles on Charcoal -- 9.3.3 Poly(ethylene glycol)-Stabilized Cobalt Nanoparticles -- 9.4 Bimetallic Nanoparticle Catalysts -- 9.4.1 Immobilized Heterobimetallic Ru/Co Nanoparticle.

9.4.2 Heterobimetallic Co/Rh Nanoparticles13 -- 9.5 Sequential Action of Two Different Catalysts in One-Pot Reactions -- 9.5.1 Chiral Pd(II) Complex and Bulk Cobalt on Charcoal-Catalyzed Tandem Asymmetric Allylic Alkylation and PK Annulation Reactions -- 9.5.2 Pd(II) Complex and Cobalt Nanoparticle-Catalyzed Three-Step One-Pot Synthesis of Fenestranes -- 9.5.3 Palladium and Cobalt Nanoparticles-Catalyzed Tandem Allylic Alkylation and PKRs -- 9.6 Conclusion -- References -- 10. Other Transition Metal-Mediated Cyclizations Leading to Cyclopentenones -- 10.1 Introduction and Background -- 10.2 [4+1] Strategies for the Synthesis of Cyclopentenones -- 10.3 [3+2] Strategies for the Synthesis of Cyclopentenones -- 10.3.1 Iron Promoted Reactions -- 10.3.2 Synthesis of Cyclopentenones via [3+2] Cycloadditions of Fisher Alkenyl Complexes -- 10.4 Nickel(0) and Palladium(0) Synthesis of Cyclopentenones -- 10.5 Metal Carbine Strategies for the Synthesis of Cyclopentenones -- 10.5.1 Cyclopropylcarbene Chromium Complexes -- 10.5.2 Rhodium(II)-Catalyzed Strategies -- 10.6 Other Methodologies -- 10.7 Conclusions -- Experimental -- References and Notes -- Index.