臺灣博碩士論文加值系統

Transition-metal-catalyzed C‒C bond formation reaction by uniting readily available π-components is an attractive strategy to synthesis biologically important compounds in a single operation with high atom-efficacy. Particularly, coupling of alkynes with various π-components is a competent method to synthesis functionalized alkenes in a highly regio- and stereoselective manner. In this regard, this thesis describes six new reactions that focus on the coupling of alkynes with alkenes, which were successfully achieved by tuning different kinds of ligands in the presence of air stable nickel- and cobalt catalyst system. For better understanding, I divided this thesis into five chapters. The first two chapters describe about cobalt- and nickel-catalyzed reductive coupling reactions of alkynes and alkenes. The third and fourth chapters describe about nickel-catalyzed three-component coupling of alkene and alkyne with bis(pinacolato)diboron and organoboronic acids. The final chapter deals with the cobalt-catalyzed enyne coupling reaction of vinyl arenes with alkynes.

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ABSTRACT III
LIST OF SCHEMES V
LIST OF TABLES VII
ABBREVIATIONS IX
LIST OF PUBLICATIONS XI
CHAPTER 1: Synthesis of trans-Disubstituted Alkenes by Cobalt Catalyzed Reductive Coupling of Terminal Alkynes with Activated Alkenes 1
1.1 General Introduction 2
1.2 Introduction 4
1.3 Results and Discussion 9
1.4 Proposed Mechanism 23
1.5 Conclusion 24
1.6 Experimental Section 25
1.7 Spectroscopic Data 27
1.8 References 45
CHAPTER 2: Nickel-Catalyzed Regio- and Stereoselective Reductive Coupling of Activated Bicyclic Alkenes with Enones and Electron-rich Alkynes 49
2.1 Introduction 50
2.2 Results and Discussion 56
2.3 Proposed mechanism for the reductive coupling of heterobicyclic alkenes with enones 61
2.4 Proposed mechanism for the reductive coupling of heterobicyclic alkenes with alkynes 68
2.5 Conclusion 69
2.6 Experimental Section 70
2.7 Spectroscopic Data 74
2.8 NOE Data 86
2.9 References 87

CHAPTER 3: Nickel Catalyzed Borylative Coupling of Alkynes with Enones and Bis(pinacolato)-diboron: A Novel Route to Substituted Alkenylboronates 90
3.1 Introduction 91
3.2 Results and Discussion 94
3.3 Proposed Mechanism 102
3.4 Conclusion 103
3.5 Experimental Section 105
3.6 Spectroscopic Data 106
3.7 NOE Data 118
3.8 References 122
CHAPTER 4: Nickel-Catalyzed Three Components Coupling of Oxabicyclic Alkenes and Alkynes with Organoboronic Acids 125
4.1 Introduction 126
4.2 Results and Discussion 127
4.3 Proposed Mechanism 136
4.4 Conclusion 137
4.5 Experimental Section 138
4.6 Spectroscopic Data 140
4.7 NOE Data 150
4.8 References 151
CHAPTER 5: Cobalt-Catalyzed Regio- and Stereoselective Intermolecular Enyne Coupling: an Efficient Route to 1,3-Diene Derivatives 153
5.1 Introduction 154
5.2 Results and Discussion 163
5.3 Proposed Mechanism 170
5.4 Conclusion 170
5.5 Experimental Section 171
5.6 Spectroscopic Data 173
5.7 NOE Data 182
5.8 References 183
Copies of 1H & 13C NMR spectra 185

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