The Pauson-Khand reaction: scope, variations and applications
Scope, Variations and Applications

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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 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.
List of Contributors xi

Foreword xiii

Preface xv

1. The Pauson-Khand reaction - an Introduction 1

Professor 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. Peric`as

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

Tanakori 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 Usingin-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

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

Professor 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 ChiralO-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...