Ramon Rios Torres

The Pauson-Khand Reaction

Scope, Variations and Applications

• Gebundenes Buch

Produktbeschreibung

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 reactions

- non chiral intramolecular and intermolecular versions of Pauson-Khand reactions

- asymmetric Pauson-Khand reaction using chiral auxiliaries

- the enantioselective Pauson-Khand reaction

- Pauson-Khand reactions catalysed by metals other than cobalt

- unconventional Pauson-Khand reactions

- the Pauson-Khand reaction in total synthesis

Presenting a comprehensive overview of this fundamental reaction, The Pauson-Khand Reaction will find a place on the bookshelves of any organic or organometallic chemist.

Produktdetails

• Verlag: Wiley & Sons
• 1. Auflage
• Seitenzahl: 336
• Erscheinungstermin: 30. April 2012
• Englisch
• Abmessung: 246mm x 173mm x 20mm
• Gewicht: 666g
• ISBN-13: 9780470970768
• ISBN-10: 0470970766
• Artikelnr.: 35046819

Autorenporträt

Professor Ramon Rios Torres, Dept Química Orgànica, Universitat de Barcelona, Spain Ramon Rios Torres was born in 1974 in Barcelona. He obtained his PhD under the supervision of Professor Albert Moyano in 2000 at the University of Barcelona, and undertook postdoctoral work with Professor P. J. Walsh at Pennsylvania University, Professor Benjamin List at Max Plank Institute, Armando Cordova at Stockholm University and Professor Alvarez-Pez at Granada, and an industrial experience at J.C. Uriach (Spain). He received an ICREA position as independent researcher in 2008 at University of Barcelona. His research interests are devoted to the discovery of new asymmetric methodologies and their applications to organic synthesis.?He is author or coauthor of more than 60 papers, 11 book chapters and 1 patent.

Inhaltsangabe

List of Contributors xi Foreword xiii Preface xv 1. The Pauson-Khand
Reaction - an Introduction 1 William J. Kerr 1.1 The Discovery and Early
Evolution of the Khand Reaction 1 1.2 The Intermolecular Pauson-Khand
Reaction 4 1.2.1 Regioselectivity of Alkyne Insertion 5 1.2.2
Regioselectivity of Alkene Insertion 6 1.3 The Intramolecular Pauson-Khand
Reaction 8 1.4 Enhancing the Pauson-Khand Annulation by Reaction Promotion
9 1.4.1 Dry State Adsorption 9 1.4.2 Ultrasound Techniques 10 1.4.3
Microwave Promotion 10 1.4.4 Amine N-Oxide Additives 11 1.4.5 Sulfide
Promoters 13 1.5 Catalytic Pauson-Khand Protocols 15 1.6 Concluding Remarks
16 Acknowledgements 17 References 17 2. The Mechanism of the Pauson-Khand
Reaction: Hypothesis, Experimental Facts, and Theoretical Investigations 23
Xacobe C. Cambeiro and Miquel A. Pericás 2.1 Introduction 23 2.2
Stoichiometric Pauson-Khand Reaction 25 2.2.1 The Ligand Substitution Steps
25 2.2.2 Cobaltacycle Formation 29 2.2.3 CO Insertion 31 2.2.4 Reductive
Elimination 32 2.3 Catalytic Pauson-Khand Reaction 32 2.4 Theoretical
Studies 33 2.4.1 General Approach to the Mechanism 33 2.4.2
Regioselectivity. Early Steps of the Pauson-Khand Reaction 37 2.4.3
Stereoselectivity 41 2.5 Conclusions 46 References 46 3. Non Chiral
Pauson-Khand Reaction 49 Takanori Shibata 3.1 History of Co-Mediated
Pauson-Khand Reaction 49 3.2 Mechanism of the Pauson-Khand Reaction 50 3.3
An Early Example of Catalytic Reaction 51 3.4 Catalytic Reactions by Aid of
Additives 52 3.5 Catalytic Reaction Using in-situ Generated Low-Valent
Cobalt Complex 55 3.6 Catalytic Reaction Using Multinuclear Cobalt Carbonyl
Catalysts 59 3.7 Catalytic Reaction Using Heterogeneous Catalysts 61 3.8
Catalytic Reaction in Other Than Conventional Solvents 63 3.9
Intramolecular Reaction of Carbodiimides with Alkynes 65 References 66 4.
Diastereoselective Pauson-Khand Reaction using Chiral Pool Techniques
(Chiral Substrates) 69 Martin Kamlar, Jan Vesely, and Ramon Rios Torres 4.1
Introduction and Background 69 4.2 Intramolecular Diastereoselective
Pauson-Khand Reaction 70 4.3 Intermolecular Diastereoselective Pauson-Khand
Reaction 87 4.4 Conclusion 90 References 91 5. Asymmetric Intra- and
Intermolecular Pauson-Khand Reactions: The Chiral Auxiliary Approach 95
Albert Moyano 5.1 Introduction 96 5.2 Asymmetric Intramolecular PKRs with
the Aid of Chiral Auxiliaries 99 5.2.1 Chiral Alkoxyacetylenes 99 5.2.2
Chiral Acetylene Thioethers 104 5.2.3 Chiral 2-alkynoate Derivatives 106
5.2.4 Chiral O-alkyl Enol Ethers 108 5.2.5 Alkenyl sulfoxides 113 5.2.6
Asymmetric Intramolecular PKRs Mediated by Chiral Auxiliaries Located in
the Enyne Tether 114 5.3 Asymmetric Intermolecular PKRs with the Aid of
Chiral Auxiliaries 116 5.3.1 Chiral Alkoxyacetylenes 116 5.3.2 Chiral
Acetylene Thioethers 124 5.3.3 Alkynyl Sulfoxides 125 5.3.4 Chiral Ynamines
and Ynamides 126 5.3.5 Chiral 2-alkynoates 128 5.3.6 Alkenyl Sulfoxides 135
5.4 Chiral Reagents for the Kinetic Resolution of PK Cycloadducts 138 5.5
Conclusion 140 Acknowledgements 140 References 140 6. The Enantioselective
Pauson-Khand Reaction 147 Agustí Lledó, Xavier Verdaguer and Antoni Riera
6.1 Introduction 148 6.2 Mechanistic Considerations. Topology of
Alkyne-Dicobalt Clusters 148 6.3 Intrinsically Chiral Dicobalt Clusters 150
6.3.1 Resolution of Monophosphine Complexes 150 6.3.2 Synthesis of Chiral
Monophosphine Complexes Using Chiral N-Oxides 151 6.3.3 Heterobimetallic
Complexes 151 6.4 Chiral Promoters 153 6.4.1 Sulfoxides 153 6.4.2 Chiral
N-Oxides 153 6.5 Chiral Ligands 155 6.5.1 Sulfides 155 6.5.2
Cyclopentadienes (Heterobimetallic) 156 6.5.3 C-Chiral and Axially Chiral
Phosphines 156 6.5.4 C2-Symmetric Bridging Bis-phosphines 161 6.5.5
C-Chiral Bidentate (P,S) Ligands 162 6.5.6 S-Chiral Bidentate (P,S) Ligands
167 6.6 Synthetic Applications 171 6.7 Conclusion 176 References 176 7.
Recent Advancement of Catalytic Pauson-Khand-type Reactions 181 Fuk Loi
Lam, Hang Wai Lee, Jun Wang and Fuk Yee Kwong 7.1 Introduction 181 7.2
Rhodium-Catalyzed Pauson-Khand-Type Cyclizations 182 7.3 Iridium-Catalyzed
Pauson-Khand-Type Cyclizations 194 7.4 Titanium-Catalyzed Pauson-Khand-Type
Cyclizations 198 7.5 Ruthenium-Catalyzed Pauson-Khand-Type Cyclizations 200
7.6 Nickel- and Palladium-Catalyzed Pauson-Khand-Type Cyclizations 201 7.7
Tandem Reactions and Miscellaneous (other than Co complex) 204 7.8
Conclusion 206 Acknowledgements 206 References 206 8. Recent Adventures
with the Pauson-Khand Reaction in Total Synthesis 211 Scott G. Van Ornum,
Sarah Hoerner and James M. Cook 8.1 Introduction 212 8.2 (+)-Epoxydictymene
212 8.3 (±)-Pentalenene and (-)-Pentalenene 214 8.4 The Tandem Pauson-Khand
Reaction Directed Towards the Synthesis of Dicyclopentapentalenes 215 8.5
Enantioselective Total Synthesis of (-)--Kainic Acid 219 8.6 The Total
Synthesis of Paecilomycine A 220 8.7 The Total Synthesis of
(+)-Achalensolide 221 8.8 The Total Synthesis of (-)-Alstonerine 222 8.9
The Total Synthesis of (±)-8-Hydroxystreptazolone 224 8.10 The Formal Total
Synthesis of (±)-- and -Cedrene 226 8.11 Additional Applications of the
Pauson-Khand Reaction in Total Synthesis 227 8.12 Conclusions 230
Acknowledgements 231 References 231 9. Heterogeneous Catalytic Pauson-Khand
Reaction 239 Young Keun Chung 9.1 Introduction 240 9.2 Development of
Heterogeneous Catalysts for PKR 240 9.2.1 Polymer-Supported Catalytic
Systems 241 9.2.2 Bulk Cobalt as a Catalyst 242 9.2.3 Raney Cobalt 243
9.2.4 Mesoporous Organized Zirconium Oxide Silica Powders as Catalyst 244
9.2.5 Mesoporous Graphitic Carbon as a Promoter 245 9.3 Transition Metal
Nanoparticle Catalyst 246 9.3.1 Colloidal Cobalt Nanoparticles 247 9.3.2
Cobalt Nanoparticles on Charcoal 247 9.3.3 Poly(ethylene glycol)-Stabilized
Cobalt Nanoparticles 249 9.4 Bimetallic Nanoparticle Catalysts 250 9.4.1
Immobilized Heterobimetallic Ru/Co Nanoparticle 250 9.4.2 Heterobimetallic
Co/Rh Nanoparticles 251 9.5 Sequential Action of Two Different Catalysts in
One-Pot Reactions 261 9.5.1 Chiral Pd(II) Complex and Bulk Cobalt on
Charcoal-Catalyzed Tandem Asymmetric Allylic Alkylation and PK Annulation
Reactions 262 9.5.2 Pd(II) Complex and Cobalt Nanoparticle-Catalyzed
Three-Step One-Pot Synthesis of Fenestranes 262 9.5.3 Palladium and Cobalt
Nanoparticles-Catalyzed Tandem Allylic Alkylation and PKRs 264 9.6
Conclusion 265 References 266 10. Other Transition Metal-Mediated
Cyclizations Leading to Cyclopentenones 275 Ramon Rios Torres and Jan
Vesely 10.1 Introduction and Background 276 10.2 [4+1] Strategies for the
Synthesis of Cyclopentenones 278 10.3 [3+2] Strategies for the Synthesis of
Cyclopentenones 283 10.3.1 Iron Promoted Reactions 283 10.3.2 Synthesis of
Cyclopentenones via [3+2] Cycloadditions of Fisher Alkenyl Complexes 284
10.4 Nickel(0) and Palladium(0) Synthesis of Cyclopentenones 285 10.5 Metal
Carbine Strategies for the Synthesis of Cyclopentenones 289 10.5.1
Cyclopropylcarbene Chromium Complexes 289 10.5.2 Rhodium(II)-Catalyzed
Strategies 291 10.6 Other Methodologies 292 10.7 Conclusions 298
Experimental 299 References and Notes 299 Index 307