臺灣博碩士論文加值系統

近年來，過渡金屬催化碳－氫鍵活化反應逐漸受到重視，因此類型反應具有高位向選擇性、不須使用官能基化之反應物、高原子經濟性且可應用於合成具生物活性之有機分子，使碳－氫鍵活化反應成為熱門的研究領域之一。於此論文中主要探討銠金屬催化於有氧環境中的分子間與分子內碳－氫鍵官能基化反應，以下分成三個章節以詳細敘述之：

第一章探討銠金屬催化2-芳基吡啶與烯化合物於氧氣下，使用純水作為溶劑，合成異吲哚啉鹽化合物。此反應中銠金屬會進行鄰位碳－氫鍵活化烯化反應，並經由氮雜－麥可加成反應、烯上β－碳去氫化與二次麥可加成，生成產物異吲哚啉鹽衍生物。

第二章敘述銠金屬催化苯甲醛與炔胺化合物進行碳－氫鍵活化與環化反應，合成異吲哚啉鹽、喹嗪鹽與吡啶并氮雜卓鹽衍生物。此合成方法成功應用於合成天然物Ficuseptine。

最後一章則講述銠金屬催化N-烷基苯甲醯胺與炔化合物於水相中與氧氣下合成高選擇性之異喹啉酮化合物。此反應可應用於較環保的合成具生物活性之含異喹啉酮骨架衍生物

In recent year transition-metal-catalyzed C‒H activation reaction got considerable attention because of catalytic reaction does not require pre-functionalization also desired product is highly regioselective and utility of reaction can be applicable to synthesis biologically important compounds in one pot operation with high atom-efficacy. In this thesis, aerobic rhodium–catalyzed inter and intra molecular C‒H Bond functionalization reactions are described. For better understanding, I divided this thesis into three chapters. The first chapter describe about rhodium-catalyzed ortho olefination via intramolecular aza-michael addition in water and oxygen as a sole oxidant. In chapter second rhodium catalyzed intramolecular C‒H activation/annulation of aldehydes with alkyne-amines demonstrated in presence of oxygen as an oxidant. The third chapter describe about synthesis of isoquinolones from N-alkyl benzamides and alkynes using Rh(III) catalyst and inexpensive oxygen as the sole oxidant in aqueous medium.

Chapter 1 describes a new method for the synthesis of Isoindolium Salts from from 2-arylpyridines and alkenes in aqueous medium under oxygen via Rh(III) catalysis. A reaction mechanism involving an ortho CH olefination of 2-arylpyridine by alkene, intramolecular aza-michael addition, deprotonation at the -carbon of the alkene fragment followed by another michael addition to give the final product is proposed.

Chapter 2 deals with the synthesis of indolizidinium, quinolizinium and pyrido[1,2-a]azepinium salts synthesized from benzaldehydes (or ,-unsaturated aldehydes) and alkyne-amines catalyzed by rhodium complex via C–H activation is demonstrated. The present method is successfully applied to the synthesis of natural product, ficuseptine.

Chapter 3 illustrates a new approach for highly regioselective synthesis of isoquinolones from N-alkyl benzamides and alkynes using Rh(III) catalyst and inexpensive oxygen as the sole oxidant in aqueous medium, in addition the methodology can be applied to the preparation of biologically active compounds having the isoquinolone core.

TABLE OF CONTENTS
Page
ABSTRACT V
LIST OF SCHEMES IX
LIST OF TABLES XIII
LIST OF FIGURES XIV
ABBREVIATIONS XV
LIST OF PUBLICATIONS XVIII

CHAPTER 1: Rh-Catalyzed Regioselective Synthesis of Isoindolium Salts from 2-Arylpyridines and Alkenes in Aqueous Medium under Oxygen 1

1.1 Introduction 3
1.2 Results and Discussion 9
1.2.1 Optimization Studies 9
1.2.2 Scope of the Reaction 11
1.3 Mechanistic Studies 16
1.4 Proposed Catalytic cycle 20
1.5 Conclusion 21
1.6 Experimental Section 22
1.7 Spectroscopic Data 28
1.8 References 46

CHAPTER 2: Facile One-Pot Synthesis of 2,3-Dihydro-1H-indolizinium Derivatives by Rhodium(III)-Catalyzed Intramolecular Oxidative Annulation via C–H Activation: Application to Ficuseptine Synthesis 50

2.1 Introduction 52
2.2 Results and Discussion 62
2.2.1 Optimization Studies 62
2.2.2 Scope of the Reaction 64
2.3 Mechanistic Discussion 69
2.4 Inter- and intra-molecular Rh-catalyzed annulation reaction. 70
2.5 Application to the Synthesis of Ficuseptine 72
2.6 Conclusion 73
2.7 Experimental Section 74
2.8 Spectroscopic Data 77
2.9 References 93

CHAPTER 3: Synthesis of Isoquinolones via Rh-Catalyzed CH/NH Activation of Substituted Benzamides Using Air as the Sole Oxidant in Water. 97

3.1 Introduction 99
3.2 Results and Discussion 107
3.2.1 Optimization Studies 107
3.2.2 Scope of the Reaction 109
3.3 Intermolecular Competition Experiment 113
3.4 Mechanistic Studies 118
3.5 Proposed Catalytic Cycle 120
3.6 Application Towards Treatment of Cardiac Atrial Fibrillation 121
3.7 Gram-Scale Reaction 122
3.8 Evaluation of Green metrics of the process 122
3.9 Conclusion 125
3.10 Experimental Section 125
3.11 Spectroscopic Data 132
3.12 References 148
Crystal Structures, 1H and 13C NMR Spectra 152

References:
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