臺灣博碩士論文加值系統

In this thesis, Palladium-catalyzed C-H bond functionalization reactions and their application in organic synthesis are discussed in detail. For convenience and better clarity, the thesis is divided into five chapters. The first chapter deals with the synthesis of fluorenone derivatives, the second chapter depicts the synthesis of diarylmethylidenefluorenes and phenanthrenes, the third chapter developed the preparation of fluorenones, fourth chapter described synthesis of indenone derivatives and fifth chapter explain the arylation of unactivated sp3 and sp2 C H bonds with aryl halides.
The synthesis of fluorenones from aromatic aldoxime ethers and aryl halides via palladium catalyzed dual C H activation and Heck cyclization are investigated in chapter 1. The reaction of benzaldehyde oxime ethers and aryl halides in presence of palladium-catalyst to gave fluorenones in good yield. This reaction proceeds in one pot. The proposed mechanism is strongly supported by the isolation of an anionic palladacycle and an intermediate organic compound. In the second chapter a useful and efficient method for the construction of diarylmethylidenefluorenes and phenanthrenes is described. The reaction of acetophenone oxime ethers with electron donating arly halides in the presence of palladium catalyst to gave phenanthrene derivatives in good yield. Similarly, acetophenone oxime ethers with electron withdrawing arly halides to gave diarylmethylidenefluorene derivatives in moderate to good yield.
Palladium-catalyzed multiple C-H functionalization to the synthesis of fluorenones from aryl aldoxime ethers with arenes by palladium complex has been described in chapter 3. The reaction of benzaldehyde oxime ethers with simple arenes by palladium complex afforded fluorenones in good to excellent yield. In the fourth chapter indenone synthesis from benzophenone oxime ethers with alkene is desicribed. In this reaction there are two tandem steps namely C-H bond olefination and cyclization. Palladium catalyzed selective arylation of unactivated sp3 and sp2 C H bond with aryl halides has been described in chapter 5.

ACKNOWLEDGEMENT iii
ABSTRACT v
LIST OF SCHEME vii
LIST OF TABLES ix
ABBREVIATIONS x
LIST OF MAJOR PUBLICATIONS xii

CHAPTER 1: Synthesis of Fluorenones from Aromatic Aldoxime
Ethers and Aryl Halides via Palladium-Catalyzed
Dual C-H Activation and Heck Cyclization

1.1 Introduction 2
1.2 Results and Discussions 11
1.3 Mechanistic Discussion 17
1.4 Conclusion 20
1.5 Experimental Section 20
1.6 Spectroscopic Data 25
1.7 References 34

CHAPTER 2: One Pot Synthesis of Diarylmethylidenefluorenes
and Phenanthrenes by Palladium Catalyzed Multiple
C H Bond Functionalization

2.1 Introduction 38
2.2 Results and Discussions 43
2.3 Mechanistic Discussion 49
2.4 Conclusion 53
2.5 Experimental Section 53
2.6 Spectroscopic Data 56
2.7 References 68



CHAPTER 3: Pd-Catalyzed Multiple C-H Functionalization to
Construct Biologically Active Compounds from
Aryl Aldoxime Ethers with Arenes

3.1 Introduction 72
3.2 Results and Discussions 79
3.3 Mechanistic Discussion 86
3.4 Conclusion 89
3.5 Experimental Section 89
3.6 Spectroscopic Data 91
3.7 References 102

CHAPTER 4: Synthesis of Indenone Derivatives: Pd-Catalyzed
C H Bond Activation of Aromatic Ketoxime
Ethers Followed by Olefination

4.1 Introduction 108
4.2 Results and Discussions 118
4.3 Mechanistic Discussion 125
4.4 Conclusion 126
4.5 Experimental Section 127
4.6 Spectroscopic Data 128
4.7 References 141

CHAPTER 5: Palladium Catalyzed Selective Arylation of
Unactivated sp3 and sp2 C H Bond with Aryl
Halides

5.1 Introduction 146
5.2 Results and Discussions 149
5.3 Mechanistic Discussion 156
5.4 Conclusion 157
5.5 Experimental Section 157
5.6 Spectroscopic Data 158
5.7 References 167
CRYSTAL STRUCTURES, 1H AND 13C NMR SPECTRA 171

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