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New Reaction Development with Organometallic Catalyst: Part I. Amide Synthesis Using Catalytic Alcohol Activation Strategy Part II. Visible Light Photoredox Catalyst Mediated C(sp3)−H Functionalization : 유기금속촉매를 이용한 유기반응 개발: Part I. 촉매적 알코올 활성화 전략을 이용한 아마이드 합성 Part II. 가시광선 광촉매를 이용한 C(sp3)-H 결합 활성화

DC Field Value Language
dc.contributor.advisorSoon Hyeok Hong-
dc.contributor.author강병준-
dc.date.accessioned2018-11-12T00:58:38Z-
dc.date.available2018-11-12T00:58:38Z-
dc.date.issued2018-08-
dc.identifier.other000000151659-
dc.identifier.urihttps://hdl.handle.net/10371/143204-
dc.description학위논문 (박사)-- 서울대학교 대학원 : 자연과학대학 화학부, 2018. 8. Soon Hyeok Hong.-
dc.description.abstractThe research described in this thesis covers development of new organic reactions catalyzed by organometallic complexes. The thesis is divided into two parts according to the catalytic strategy used. Part I introduces a new catalytic amide synthetic method utilizing dehydrogenative alcohol activation strategy. It is atom-economical and environmentally benign alternative of classical amide synthetic strategies. The basic concept of the strategy and state-of-the-art examples are discussed in Chapter 1. 100% atom economical amide synthesis using alcohols and nitriles as reactant is achieved with N-heterocyclic carbene (NHC) coordinated ruthenium catalyst (Chapter 2). NHC-dihydridoruthenium complex is proposed as the active catalytic species, and the involvement of unusual imine intermediate is suggested based on the mechanistic studies. Methanol is a promising C1 building block due to its low toxicity, low cost, and worldwide stabilized production. With well-defined NHC-dihydridoruthenium catalyst, N-formamide is synthesized from either nitrile or amine utilizing methanol as a formylating source (Chapter 3). No extra base or hydrogen acceptor is required.

Part II describes C(sp3)−H activation reactions mediated by visible light photoredox catalysis. C(sp3)−H functionalization is an ideal process in organic chemistry. Recent advance in visible light photoredox catalysis enables selective and efficient C(sp3)−H activation reactions. The concept of the strategy and representative examples are summarized in Chapter 4. Thioesters are versatile synthetic building blocks of complex molecule synthesis and peptide synthesis. The photoredox mediated nickel catalyzed ethereal C(sp3)−H thiocarbonylation reaction is reported (Chapter 5). It is not only the first C(sp3)–H thiocarbonylation reaction, but also the first example of utilizing simple aryl thioester as a thiocarbonylation source instead of CO gas and thiol. Photocatalytic single electron reduction and fragmentation of the thioester is proposed as the key mechanism of the reaction.
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dc.description.tableofcontentsAbstract 1

Table of Contents 4

List of Tables 8

List of Schemes 9

List of Figures 12

Appendix 186

Abstract in Koreans 277



Part I. Amide Synthesis Using Catalytic Alcohol Activation Strategy 13

Chapter 1. Amide Synthesis from Alcohol and Amine Using Dehydrogenative Alcohol Activation Strategy 13

1.1 Introduction 13

1.2 Conventional amide bond synthesis 13

1.3 Amide synthesis with catalytic dehydrogenative alcohol activation 16

1.3.1 Dehydrogenative alcohol activation 16

1.3.2 Amide synthesis with catalytic dehydrogenative alcohol activation: Ru and Rh based catalysts 20

1.3.3 Amide synthesis with catalytic dehydrogenative alcohol activation: Fe and Mn based catalysts 31

1.4 Conclusion 34

1.5 References 35

Chapter 2. Ruthenium-Catalyzed Redox-Neutral and Single-Step Amide Synthesis from Alcohol and Nitrile with Complete Atom Economy 39

2.1 Introduction 39

2.2 Results and discussion 41

2.2.1 Optimization for amide synthesis from alcohol and nitrile 41

2.2.2 Substrate scope 43

2.2.3 Mechanistic studies 49

2.3 Conclusion 54

2.4 Experimental section 54

2.4.1 General information 54

2.4.2 General procedure for amide synthesis from nitrile and alcohol 55

2.4.3 Procedure for deuterium labeling study 56

2.4.4 GC analysis for reaction intermediate detection 56

2.4.5 1H NMR experiment for benzaldimine intermediate observation 58

2.4.6 Characterization of newly reported compounds 62

2.5 References 69

Chapter 3. Hydrogen Acceptor- and Base-Free N-Formylation of Nitriles and Amines Using Methanol as C1 Source 72

3.1 Introduction 72

3.2 Results and discussion 75

3.2.1 Reaction condition optimization 75

3.2.2 Substrate scope of nitrile 78

3.2.3 Mechanistic studies 81

3.2.4 Substrate scope of amine 83

3.3 Conclusion 86

3.4 Experimental section 87

3.4.1 General information 87

3.4.2 General procedure for N-formamide synthesis from nitrile and methanol 87

3.4.3 General procedure for N-formamide synthesis from amine and methanol 88

3.4.4 Investigation of reaction intermediates 88

3.4.5 Characterization of newly reported compounds 89

3.5 References 97

Part II. Visible Light Photoredox Catalyst Mediated C(sp3) H Functionalization 100

Chapter 4. Visible Light Photoredox Catalysis for C(sp3)H Functionalization 100

4.1 Introduction 100

4.2 Concept and general mechanism of visible light photoredox catalysis 101

4.3 Visible light photoredox α-amino C(sp3)H functionalization 105

4.4 Visible light photoredox C(sp3)H functionalization with hydrogen atom transfer (HAT) catalysis 114

4.5 Visible light photoredox C(sp3)H functionalization with transition metal catalysis 118

4.6 Visible light photoredox/transition metal/HAT triple catalysis 124

4.7 Conclusion 126

4.8 References 127

Chapter 5. Photoredox Mediated Nickel Catalyzed C(sp3)H Thiocarbonylation of Ethers 132

5.1 Introduction 132

5.2 Results and discussion 134

5.2.1 Optimization for α-oxy thiocarbonylation reaction 134

5.2.2 Substrate scope of thioesters 136

5.2.3 Substrate scope of ethers 138

5.2.4 Mechanistic studies 139

5.3 Conclusion 147

5.4 Experimental section 148

5.4.1 General information 149

5.4.2 General procedure for reactant thioester synthesis 150

5.4.3 General procedure for C(sp3)H thiocarbonylation reactions 150

5.4.4 Procedure for 13CO incorporation experiment 151

5.4.5 Deuterium incorporation experiment 154

5.4.6 Synthesis and characterization of nickel complexes 155

5.4.7 Cyclic voltammetry (CV) studies 157

5.4.8 Characterization of newly reported compounds 161

5.5 References 182




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dc.language.isoen-
dc.publisher서울대학교 대학원-
dc.subject.ddc540-
dc.titleNew Reaction Development with Organometallic Catalyst: Part I. Amide Synthesis Using Catalytic Alcohol Activation Strategy Part II. Visible Light Photoredox Catalyst Mediated C(sp3)−H Functionalization-
dc.title.alternative유기금속촉매를 이용한 유기반응 개발: Part I. 촉매적 알코올 활성화 전략을 이용한 아마이드 합성 Part II. 가시광선 광촉매를 이용한 C(sp3)-H 결합 활성화-
dc.typeThesis-
dc.contributor.AlternativeAuthorKang, Byungjoon-
dc.description.degreeDoctor-
dc.contributor.affiliation자연과학대학 화학부-
dc.date.awarded2018-08-
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