The Pauson-Khand Reaction Scope, Variations and Applications

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ISBN: 9780470970768 | 0470970766
Cover: Hardcover
Copyright: 4/30/2012

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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 PausonKhand-type reactions non chiral intramolecular and intermolecular versions of PausonKhand reactions asymmetric PausonKhand reaction using chiral auxiliaries the enantioselective PausonKhand reaction PausonKhand reactions catalysed by metals other than cobalt unconventional PausonKhand reactions the PausonKhand 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.

List of Contributors	p. xi
Foreword	p. xiii
Preface	p. xv
The Pauson-Khand Reaction - an Introduction	p. 1
The Discovery and Early Evolution of the Khand Reaction	p. 1
The Intermolecular Pauson-Khand Reaction	p. 4
Regioselectivity of Alkyne Insertion	p. 5
Regioselectivity of Alkene Insertion	p. 6
The Intramolecular Pauson-Khand Reaction	p. 8
Enhancing the Pauson-Khand Annulation by Reaction Promotion	p. 9
Dry State Adsorption	p. 9
Ultrasound Techniques	p. 10
Microwave Promotion	p. 10
Amine N-Oxide Additives	p. 11-
Sulfide Promoters	p. 13
Catalytic Pauson-Khand Protocols	p. 15
Concluding Remarks	p. 16
Acknowledgements	p. 17
References	p. 17
The Mechanism of the Pauson-Khand Reaction: Hypothesis, Experimental Facts, and Theoretical Investigations	p. 23
Introduction	p. 23
Stoichiometric Pauson-Khand Reaction	p. 25
The Ligand Substitution Steps	p. 25
Cobaltacycle Formation	p. 29
CO Insertion	p. 31
Reductive Elimination	p. 32
Catalytic Pauson-Khand Reaction	p. 32
Theoretical Studies	p. 33
General Approach to the Mechanism	p. 33
Regioselectivity, Early Steps of the Pauson-Khand Reaction	p. 37
Stereoselectivity	p. 41
Conclusions	p. 45
References	p. 46
Non Chiral Pauson-Khand Reaction	p. 49
History of Co-Mediated Pauson-Khand Reaction	p. 49
Mechanism of the Pauson-Khand Reaction	p. 50
An Early Example of Catalytic Reaction	p. 51
Catalytic Reactions by Aid of Additives	p. 52
Catalytic Reaction Using in-situ Generated Low-Valent Cobalt Complex	p. 55
Catalytic Reaction Using Multinuclear Cobalt Carbonyl Catalysts	p. 59
Catalytic Reaction Using Heterogeneous Catalysts	p. 61
Catalytic Reaction in Other Than Conventional Solvents	p. 63
Intramolecular Reaction of Carbodiimides with Alkynes	p. 65
References	p. 66
Diastereoselective Pauson-Khand Reaction using Chiral Pool Techniques (Chiral Substrates)	p. 59
Introduction and Background	p. 69
Intramolecular Diastereoselective Pauson-Khand Reaction	p. 70
Intermolecular Diastereoselective Pauson-Khand Reaction	p. 87
Conclusion	p. 90
References	p. 91
Asymmetric Intra- and Intermolecular Pauson-Khand Reactions: The Chiral Auxiliary Approach	p. 95
Introduction	p. 96
Asymmetric Intramolecular PKRs with the Aid of Chiral Auxiliaries	p. 99
Chiral Alkoxyacetylenes	p. 99
Chiral Acetylene Thioethers	p. 104
Chiral 2-alkynoate Derivatives	p. 106
Chiral O-alkyl Enol Ethers	p. 108
Alkenyl sulfoxides	p. 113
Asymmetric Intramolecular PKRs Mediated by Chiral Auxiliaries Located in the Enyne Tether	p. 114
Asymmetric Intermolecular PKRs with the Aid of Chiral Auxiliaries	p. 116
Chiral Alkoxyacetylenes	p. 116
Chiral Acetylene Thioethers	p. 124
Alkynyl Sulfoxides	p. 125
Chiral Ynamines and Ynamides	p. 126
Chiral 2-alkynoates	p. 128
Alkenyl Sulfoxides	p. 135
Chiral Reagents for the Kinetic Resolution of PK Cycloadducts	p. 138
Conclusion	p. 140
Acknowledgements	p. 140
References	p. 140
The: Enantioselective Pauson-Khand Reaction	p. 147
Introduction	p. 148
Mechanistic Considerations. Topology of Alkyne-Dicobalt Clusters	p. 148
Intrinsically Chiral Dicobalt Clusters	p. 150
Resolution of Monophosphine Complexes	p. 150
Synthesis of Chiral Monophosphine Complexes Using Chiral N-Oxides	p. 151
Heterobimetallic Complexes	p. 151
Chiral Promoters	p. 153
Sulfoxides	p. 153
Chiral N-Oxides	p. 153
Chiral Ligands	p. 155
Sulfides	p. 155
Cyclopentadienes (Heterobimetallic)	p. 156
C-Chiral and Axially Chiral Phosphines	p. 156
C2-Symmetric Bridging Bis-phosphines	p. 161
C-Chiral Bidentate (P,S) Ligands	p. 162
S-Chiral Bidentate (P,S) Ligands	p. 167
Synthetic Applications	p. 171
Conclusion	p. 176
References	p. 176
Recent Advancement of Catalytic Pauson-Khand-type Reactions	p. 181
Introduction	p. 181
Rhodium-Catalyzed Pauson-Khand-Type Cyclizations	p. 182
Iridium-Catalyzed Pauson-Khand-Type Cyclizations	p. 194
Titanium-Catalyzed Pauson-Khand-Type Cyclizations	p. 198
Ruthenium-Catalyzed Pauson-Khand-Type Cyclizations	p. 200
Nickel- and Palladium-Catalyzed Pauson-Khand-Type Cyclizations	p. 201
Tandem Reactions and Miscellaneous (other than Co complex)	p. 204
Conclusion	p. 206
Acknowledgements	p. 206
References	p. 206
Recent Adventures with the Pauson-Khand Reaction in Total Synthesis	p. 211
Introduction	p. 212
(+)-Epoxydictymene	p. 212
(±)-Pentalenene and (-)-Pentalenene	p. 214
The Tandem Pauson-Khand Reaction Directed Towards the Synthesis of Dicyclopentapentalenes	p. 215
Enantioselective Total Synthesis of (-)-¿-Kainic Acid	p. 219
The Total Synthesis of Paecilomycine A	p. 220
The Total Synthesis of (+)-Achalensolide	p. 221
The Total Synthesis of (-)-Alstonerine	p. 222
The Total Synthesis of (?)-8¿-Hydroxystreptazolone	p. 224
The Formal Total Synthesis of (?)-¿- and ß-Cedrene	p. 226
Additional Applications of the Pauson-Khand Reaction in Total Synthesis	p. 227
Conclusions	p. 230
Acknowledgements	p. 231
References	p. 231
Heterogeneous Catalytic Pauson-Khand Reaction	p. 239
Introduction	p. 240
Development of Heterogeneous Catalysts for PKR	p. 240
Polymer-Supported Catalytic Systems	p. 241
Bulk Cobalt as a Catalyst	p. 242
Raney Cobalt	p. 243
Mesoporous Organized Zirconium Oxide Silica Powders as Catalyst	p. 244
Mesoporous Graphitic Carbon as a Promoter	p. 245
Transition Metal Nanoparticle Catalyst	p. 246
Colloidal Cobalt Nanoparticles	p. 247
Cobalt Nanoparticles on Charcoal	p. 247
Poly(ethylene glycol)-Stabilized Cobalt Nanoparticles	p. 249
Bimetallic Nanoparticle Catalysts	p. 250
Immobilized Heterobimetallic Ru/Co Nanoparticle	p. 250
Heterobimetallic Co/Rh Nanoparticles	p. 251
Sequential Action of Two Different Catalysts in One-Pot Reactions	p. 261
Chiral Pd(II) Complex and Bulk Cobalt on Charcoal-Catalyzed Tandem Asymmetric Allylic Alkylation and PK Annulation Reactions	p. 262
Pd(II) Complex and Cobalt Nanoparticle-Catalyzed Three-Step One-Pot Synthesis of Fenestranes	p. 262
Palladium and Cobalt Nanoparticles-Catalyzed Tandem Allylic Alkylation and PKRs	p. 264
Conclusion	p. 265
References	p. 266
Other Transition Metal-Mediated Cyclizations Leading to Cyclopentenones	p. 275
Introduction and Background	p. 276
[4+1] Strategies for the Synthesis of Cyclopentenones	p. 278
[3+2] Strategies for the Synthesis of Cyclopentenones	p. 283
Iron Promoted Reactions	p. 283
Synthesis of Cyclopentenones via [3+2] Cycloadditions of Fisher Alkenyl Complexes	p. 284
Nickel(O) and Palladium(O) Synthesis of Cyclopentenones	p. 285
Metal Carbine Strategies for the Synthesis of Cyclopentenones	p. 289
Cyclopropylcarbene Chromium Complexes	p. 289
Rhodium(II)-Catalyzed Strategies	p. 291
Other Methodologies	p. 292
Conclusions	p. 298
Experimental	p. 299
References and Notes	p. 299
Index	p. 307
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