The Pauson-Khand Reaction

Name: The Pauson-Khand Reaction | Scope, Variations and Applications
Brand: Wiley
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Scope, Variations and Applications

Ramon Rios Torres(Autor*in)

Wiley (Verlag)

Erschienen am 23. Februar 2012

336 Seiten

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978-1-119-94192-7 (ISBN)

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Inhalt

Intro
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 (-)-a-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 (±)-8a-Hydroxystreptazolone
8.10 The Formal Total Synthesis of (±)-a- and ß-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

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