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研究生:卡迪克
研究生(外文):Karthikeyan
論文名稱:Cobalt-, Palladium- and Rhodium-Catalyzed C–C Bond Formations via Addition and C–H Functionalization Reactions
論文名稱(外文):鈷、鈀及銠金屬催化碳—碳鍵生成反應:碳—氫鍵官能基化及加成反應之研究
指導教授:鄭建鴻鄭建鴻引用關係
指導教授(外文):Cheng, Chien Hong
學位類別:博士
校院名稱:國立清華大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:英文
論文頁數:305
中文關鍵詞:CobaltPalladiumRhodiumAsymmetric Addition reactionsC-H bond activations
外文關鍵詞:CobaltPalladiumRhodiumAsymmetric Addition reactionsC-H bond activations
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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, asymmetric synthesis and C H bond activation reactions are competent method to synthesis biologically important compounds in a highly regio- and stereoselective manner. In this regard, this thesis describes ten new reactions that focus on the asymmetric addition of arylboronic acids with aldehydes, bicyclic alkenes, which were successfully achieved by tuning different kinds of chiral ligands in the presence of air stable cobalt catalyst system. The C H functionalization of arylboronic acids with heteroarenes and N-methoxybenzamides to afford various functionalized biaryls. On the other hand multiple C H activations of
N-methoxybenzamides with simple arenes and alkenes afforded biologically active phenanthridinone and isoindolinone derivatives in one-pot manner. For better understanding, I divided this thesis into seven chapters. The first three chapters describe about cobalt-catalyzed addition reactions of aldehydes and bicyclic alkenes with organoboronic acids. The fourth chapter describe about cobalt-catalyzed direct arylation reaction of heteroarenes with organoboronic acids. The next two chapters deal with palladium-catalyzed C-H activation reactions of N-methoxybenzamides with simple arenes and alkenes. The final chapter describe about the dual C H activations of
N-methoxybenzamides with arylboronic acids using rhodium(III) as the catalyst.

TABLE OF CONTENTS

Page
ABSTRACT IV
LIST OF SCHEMES VI
LIST OF TABLES VIII
ABBREVIATIONS X
LIST OF PUBLICATIONS XIII
CHAPTER 1: Cobalt-Catalyzed Addition Reaction of Organoboronic Acids with Aldehydes: Highly Enantioselective Synthesis of Diarylmethanols 1
1.1 General Introduction 2
1.2 Introduction to present work 5
1.3 Results and Discussion 8
1.4 Proposed Stereochemical Model 18
1.5 Conclusion 18
1.6 Experimental Section 18
1.7 Spectroscopic Data 23
1.8 HPLC Data 31
1.9 References 34
CHAPTER 2: Synthesis of Biarylketones and 3-Substituted Phthalides from Organoboronic acids and Aldehydes Catalyzed by Cobalt Complexes 37
2.1 Introduction 38
2.2 Results and Discussion 43
2.3 Proposed Mechanism for Cobalt-Catalyzed Addition Reaction of Aldehydes with Arylboronic acids 49
2.4 Conclusion 53
2.5 Experimental Section 54
2.6 Spectroscopic Data 55
2.7 References 67
CHAPTER 3: Cobalt-Catalyzed Stereoselective Ring-Opening of Oxa, Aza- and Diaza Bicyclic Alkenes with Arylboronic Acids: Synthesis of 1,2-Dihydro-1-Naphthol, 1-Naphthylamine and 3,4-disubstituted hydrazino cyclopentene Derivatives 70
3.1 Introduction 71
3.2 Results and Discussion 77
3.3 Proposed Mechanism for cobalt-catalyzed ring-opening reaction
of bicyclic alkenes with arylboronic acids 86
3.4 Proposed Mechanism for Ring opening Reaction of diazabicycle
with Organoboronic Acids. 90
3.5 Conclusion 91
3.6 Experimental Section 91
3.7 Spectroscopic Data 94
3.8 HPLC Data 107
3.9 References 108
CHAPTER 4: Cobalt Catalyzed Direct C H Arylation of Azoles with Aryl Boronic acids 111
4.1 Introduction 112
4.2 Results and Discussion 115
4.3 Proposed Mechanism 120
4.4 Conclusion 120
4.5 Experimental Section 121
4.6 Spectroscopic Data 121
4.7 References 126
CHAPTER 5: Synthesis of Phenanthridinones from
N-Methoxybenzamides and Arenes by Multiple Palladium-Catalyzed C-H Activation Steps at Room Temperature 129
5.1 Introduction 130
5.2 Results and Discussion 136
5.3 Mechanistic Discussion 143
5.4 Conclusion 144
5.5 Experimental Section 145
5.6 Spectroscopic Data 146
5.7 References 154
CHAPTER 6: Palladium Catalyzed Heterocyclization of N-Methoxy Benzamides with Alkenes under Room Temperature 157
6.1 Introduction 158
6.2 Results and Discussion 164
6.3 Mechanistic Discussion 171
6.4 Conclusion 172
6.5 Experimental Section 173
6.6 Spectroscopic Data 173
6.7 References 182
CHAPTER 7: Rh(III)-Catalyzed Oxidative C H Coupling of
N-Methoxybenzamides with Arylboronic acids: One-pot Synthesis of Phenanthridinones under Mild Conditions 184
7.1 Introduction 185
7.2 Results and Discussion 190
7.3 Mechanistic Discussion 196
7.4 Conclusion 197
7.5 Experimental Section 197
7.6 Spectroscopic Data 198
7.7 References 208
CRYSTAL STRUCTURES, 1H AND 13C NMR spectra 212

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