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dc.description.abstractThree different topics are comprised in this thesis research: Chapter 1 is the chemoselective intramolecular alkylation of the Blaise reaction intermediate for tandem one-pot synthesis of exo-cyclic enaminoesters, Chapter 2 is palladium- and copper-catalyzed chemoselective arylation for tandem one-pot synthesis of indole derivatives, and the last chapter is nitrile-mediated addition of Reformatsky reagent to non-activated 1-alkynes and 1,3-enynes involving retro-Blaise reaction, and its application to tandem one-pot de novo construction of α-arylated alkanoates. Chapter 1: The intramolecular alkylative reactivity and N/C selectivity of the various intact Blaise reaction intermediates, which are formed from the reaction of the Reformatsky reagents with ω-chloroalkyl nitriles have been investigated. The chemoselectivity may influenced stereoelectronically by the tethered length and substituent at the C-2 position. To overcome its low reactivity and poor N/C selectivity, various additives were investigated, among which the addition of NaHMDS dramatically enhanced the reactivity and N/C selectivity. Chapter 2: The compatibility of the Blaise reaction intermediate with transition metal catalyst has been investigated for the development of new tandem catalytic reactions. In section (i), novel tandem one-pot method for the synthesis of indoles and N-fused indoles from readily available nitriles and Reformastsky reagents through the Pd-catalyzed intramolecular N-arylative and N-alkylative/N-arylative trappings of the Blaise reaction intermediates has been developed. In section (ii), it has been also demonstrated that, the Cu-catalyzed intermolecular N-C/C-C coupling of the Blaise reaction intermediate with 1,2-dihaloarenes could also be an alternative approach for tandem one-pot synthesis of indoles. In last section (iii), the N/C chemoselectivity in Pd-catalyzed dimerization of Blaise reaction intermediates, formed from o-bromobenzonitriles have been investigated. It has propensity to be a N-nucleophile, and the intermolecular N-arylation of the Blaise reaction intmerdiate proceeded efficiently in high chemoselectivity. Chapter 3: Novel nitrile-mediated additions of unstabilized zinc ester enolates to 1-alkynes and 1,3-enynes have been developed. The key to this reaction is the regioselective addition of a Blaise reaction intermediate to a terminal alkyne, followed by a retro-Blaise reaction generating a zinc dienolate intermediate. This method is combined with a Diels-Alder reaction and subsequent oxidative aromatization, providing a tandem one-pot de novo synthesis of α-arylated alkanoates from α-bromo alkanoates. ;졸업 논문의 연구는 3가지의 다른 주제로 구성되어 있다. Chapter 1의 주제는 exo-cyclic enaminoester를 tandem으로 합성하기 위한 Blaise 반응 중간체의 분자내 선택적 알킬화반응에 관한 것이고, Chapter 2는 indole과 그 유도체를 합성하기 위해 Pd, Cu 촉매를 이용한 분자 내 선택적 아릴화 반응에 관한 연구이다. 마지막 Chapter 3의 주제는 nitrile을 매개채로 하여 Reformatsky reagent를 비활성의 1-alkyne과 1,3-eneyne에 첨가하는 Retro-Blaise 반응에 관한 연구이다. Chapter 1: ω-chloroalkyl nitriles로부터 합성된 Blaise 반응 중간체의 분자내 반응성과 N/C 선택성에 대해 연구하였다. 반응의 선택성은 알킬기의 길이와 C-2위치의 치환체에 따라 stereoelectronic 요인에 영향을 받았다. 낮은 반응성과 N/C선택성을 높이기 위해 다양한 첨가물을 조사하였고, 그 중 NaHMDS 존재하에서 높은 선택성과 반응성을 보였다. Chapter 2: 새로운 tandem 촉매 반응을 개발하기 위해 Blaise 반응 중간체와 전이금속촉매와의 상호보완성에 관해 연구하였다. Section (i)에서는 Pd 촉매를 이용하여 Blaise 반응중간체의 분자내 선택적 N-아릴화 반응을 통해 indole을 합성하였고, 분자내 N-알킬반응과 N-아릴화 반응을 동시에 진행하여 N-fused indole을 합성하는 새로운 방법을 개발하였다. Section (ii)에서는 Cu 촉매를 이용하여 Blaise 반응 중간체와 1,2,-dihaloarene과의 분자간 N-C/C-C coupling반응을 통해 indole 유도체를 합성하였다. 마지막 section (iii)에서는 o-bromobenzonitrile로부터 합성된 Blaise 반응 중간체의 분자간 dimerization 반응을 통해 N/C 선택성을 연구하였다. 그 결과 N-공격기가 우세하여 높은 선택성으로 분자간 N-아릴화 반응이 진행되었다. Chapter 3: nitrile을 매개채로 하여 Reformatsky reagent를 비활성의 1-alkyne과 1,3-eneyne에 첨가하는 새로운 방법에 관해 연구하였다. 이 반응의 핵심은 Blaise 반응 중간체에 높은 위치선택성으로 terminal-alkyne이 첨가되고, 뒤이어 retro-Blaise 반응이 일어나 zinc dienolate 중간체가 형성되는 것이다. 개발된 새로운 방법을 Diels-Alder 반응, 산화 아릴화 반응과 결합하여 α-arylated alkanoates를 α-bromo alkanoates로부터 tandem에 합성하는 새로운 방법을 제시하였다.-
dc.description.tableofcontentsChapter 1. Chemoselective Intramolecular Alkylation of the BRIs for Tandem One-Pot Synthesis of Exo-cyclic Enaminoesters 1 1-1. Introduction 2 1-2. Results and Discussion 4 1-3. Experiments 12 1-4. References 19 Chapter 2. Palladium- and Copper-Catalyzed Chemoselective Arylation for Tandem One-Pot Synthesis of Indole Derivatives 22 2-1. Introduction 23 2-2. Results and Discussion 30 2-3. Experiments 48 2-4. References 63 Chapter 3 Nitrile-Mediated Addition of Reformatsky Reagent to Non-activated 1-Alkynes and 1,3-Enynes involving retro-Blaise Reaction, and Its Application to Tandem One-pot de novo Construction of α-Arylated Alkanoates 69 3-1. Introduction 70 3-2. Results and Discussion 72 3-3. Experiments 81 3-4. References 102 Appendix 107 1. Appendix for Chapter 1. 108 2. Appendix for Chapter 2. 127 3. Appendix for Chapter 3. 154 국문초록 201-
dc.format.extent30151436 bytes-
dc.publisher이화여자대학교 대학원-
dc.titleDevelopment of Novel Tandem Reactions Using the Blaise Reaction Intermediate-
dc.typeDoctoral Thesis-
dc.title.subtitleThe Structural Effects of the Blaise Reaction Intermediate on the Regio- and Chemoselective Tandem C-C and C-N Bond Formation-
dc.format.pagexiii, 202 p.-
dc.identifier.major대학원 화학·나노과학과- 2-
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