Pauson-Khand Reaction - Scope, Variations and Applications

Informationen zum Autor 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. Klappentext 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, including: the mechanism of the Pauson-Khand reaction non-chiral Pauson-Khand reactions diastereoselective Pauson-Khand reactions asymmetric Pauson-Khand reactions using chiral auxiliaries enantioselective Pauson-Khand reactions recent advances in catalytic Pauson-Khand reactions the Pauson-Khand reaction in total synthesis heterogenous catalytic Pauson-Khand reactions other carbonylative cyclizations leading to cyclopentenones 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. Zusammenfassung The Pauson-Khand Reaction presents the first dedicated volume on this pivotal reaction and its variations, providing synthetic organic chemists with details on how to create the useful cyclopentenone unit from simple components in a highly controlled way. Inhaltsverzeichnis 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 Paus...

List of contents

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 E

Product details

• Authors: R Rios Torres, Ramon Rios Torres, Ramon (Universitat De Barcelona) Rios Torres, Rios Torres Ramon, Ramon Rios Torres
• Publisher: Wiley, John and Sons Ltd
• Languages: English
• Product format: Hardback
• Released: 13.04.2012
• EAN: 9780470970768
• ISBN: 978-0-470-97076-8
• No. of pages: 336
• Subjects: Natural sciences, medicine, IT, technology > Chemistry > Physical chemistry; Chemie, Organische Chemie, chemistry, Pharmaceutical & Medicinal Chemistry, Pharmazeutische u. Medizinische Chemie, Methods - Synthesis & Techniques, Organische Chemie / Methoden, Synthesen, Verfahren, Coordination Chemistry, Koordinationschemie