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22대 대한민국 국회 국회정보길라잡이 국회의원검색
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Title Page

ABSTRACT

국문 초록

Contents

NOMENCLATURE 13

CHAPTER 1. Introduction 17

1.1. Tetrahydrofuran Derivatives 18

1.2. Direct Functionalization of THF Cores 20

1.3. Intramolecular Reaction for Synthesis of THF Derivatives 23

1.3.1. Cyclizations that Form C-C Bonds 24

1.3.2. Cyclizations that Form C-O Bonds 28

1.4. Intermolecular Reaction for Synthesis of THF Derivatives 35

1.4.1. [3+2] Cycloaddition 36

1.4.2. [4+1] Cycloaddition 45

1.4.3. [2+2+1] Cycloaddition 49

CHAPTER 2. The Synthesis of THF Derivatives via Pd-Catalyzed Oxidative Cycloaddition of Alkenes and Allyl Alcohols 51

2.1. Background and Motivation 52

2.2. Initial Hit and Identifying Diastereomers 57

2.3. Reaction Development 59

2.3.1. Optimization 59

2.3.2. Control Experiment 61

2.4. Alkene Scope 63

2.5. Proposed Mechanism 65

2.6. Gram-Scale Synthesis 67

2.7. Conclusion 68

2.8. Outlook 69

2.8.1. Reactivity of Alkenes 69

2.8.2. Reactivity of Allyl Alcohols 70

2.8.3. Asymmetric Synthesis 73

CHAPTER 3. Experimental Part 74

3.1. General Information 75

3.2. Synthesis of 4 76

3.3. Synthesis of THF derivatives 77

3.3. Detailed Optimized Table 86

REFERENCE 93

APPENDICES 107

List of Tables

Table 2.1. Optimized table 60

Table 2.2. Control experiment 62

Table 2.3. Alkene scope 64

Table 2.4. Screening of other alkenes 69

Table 2.5. Screening of allyl alcohols 71

Table 3.1. Substrate ratio 86

Table 3.2. DMSO loading 86

Table 3.3. Sulfoxide additive screening 87

Table 3.4. HFIP loading 87

Table 3.5. Catalyst screening 88

Table 3.6. Oxidant screening 89

Table 3.7. Additive screening 90

Table 3.8. Solvent screening 91

Table 3.9. Reaction temperature 92

Table 3.10. Reaction time 92

List of Figures

Figure 1.1. THF-containing natural products and pharmaceuticals 19

Figure 1.2. Possible disconnections of THFs by cleavage one bonds 23

Figure 1.3. Possible disconnections of THFs into 2 or 3 components 35

Figure 2.1. General mechanism of wacker oxidation 53

Figure 2.2. Proposed mechanism 66

Figure 3.1. Sulfoxide additives 87

List of Schemes

Scheme 1.1. Challenge of direct generation of anionic cyclic ether 20

Scheme 1.2. Selective direct functionalization of THFs 22

Scheme 1.3. Selective olefin metathesis reaction 25

Scheme 1.4. Cycloisomerization for THF 27

Scheme 1.5. General C-O formation methods 28

Scheme 1.6. Selective nucleophilic substitution reaction 30

Scheme 1.7. Selective alkene functionalization reaction 32

Scheme 1.8. Dehydrogenative annulation 34

Scheme 1.9. [3+2] cycloaddition using O-C-C fragment 38

Scheme 1.10. A) General cycloaddition of carbonyl ylide and olefin. B) Restrosynthetic strategy of carbonyl ylide 39

Scheme 1.11. Selective [3+2] cycloaddition using carbonyl ylide 41

Scheme 1.12. Selective [3+2] cycloaddition with three-carbon partner with ketone 44

Scheme 1.13. Selective [4+1] cycloaddition using diazo compounds 46

Scheme 1.14. Selective THF synthesis by oxidation of 1,5-diene 48

Scheme 1.15. Fox's [2+2+1] cycloaddition 49

Scheme 2.1. General wacker oxidation 53

Scheme 2.2. Our aim 53

Scheme 2.3. A) General strategy of cycloaddition with vinyl ether and allyl alcohol. B, C) Selective reactions of alkene and propargyl alcohol or allyl alcohol. D) This work 56

Scheme 2.4. Initial hit 58

Scheme 2.5. Synthesis of 4 in specific condition 58

Scheme 2.6. Gram-scale synthesis 67

Scheme 2.7. Reaction with cinnamyl alcohol (2z) 72

초록보기

 테트라하이드로퓨란 (THF) 모티프는 생물학적으로 활성인 분자 및 천연물에서 흔히 볼 수 있는 구조이다. 따라서 높은 입체 선택성을 갖는 다치환된 THF 구조를 효율적으로 합성하기 위한 연구들이 많이 진행되었다. 그러나 이러한 방법들은 종종 특정 기질에만 적용 가능하다는 점에서 한계가 있다. 본 연구에서는 간단한 알켄과 알릴 알코올로부터 팔라듐을 촉매로 한 산화적 고리화를 통한 트랜스-2,4-이탄소치환된 THF 의 새로운 합성법을 개발하였다. 이를 통해 높은 수율과 부분입체선택성을 가지는 THF 를 합성할 수 있었다.

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