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Mechanism of Copper Catalyzed Diazo Coupling and its Applications & Reactions of Multiynes.

機(jī)譯：銅催化重氮偶聯(lián)的機(jī)理及其在多炔的應(yīng)用與反應(yīng)

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This thesis has two main parts. Part I is composed of two chapters which describes mechanistic investigation of copper catalyzed reactions of diazo compounds followed by their applications in click chemistry. Part II consists of three chapters describing new methods for the generation of functionalized arenes from multiynes via transition metal catalyzed reactions.;Chapter 1 consists of the mechanistic study of copper catalyzed reaction of diazo compounds with terminal alkynes. In this work, with the help of kinetic preference of the catalyst, crossover experiments data and hammett plots, we gathered substantial evidence for the copper acetylide mechanism over the Cu-carbenoid-mediated C--H insertion mechanism for the reaction between terminal alkyne and diazo compounds with CuI. Chapter 2 describes a novel three component coupling reaction for the preparation of 1,4,5-trisubstituted-1,2,3-triazoles by in-situ trapping of 5-copper-1,2,3-triazole intermediate with diazo compounds. Selected examples are highlighted to demonstrate the scope of the reaction along with the electronic effects of the alkyne and azides on the three component coupling reaction. This methodology is further extended for the preparation of fused triazole motifs in a single step.;In part II, chapter 3 discuss a brief survey in the recent developments of HDDA based aryne chemistry and its applications. Chapter 4 discloses an unprecedented dual reactivity of C--H bonds on the beta-carbon of the silyl group in the aryne intermediates. In this 2° and 3° C--H bonds to the silicon exclusively undergoes 1,5-hydride transfer, whereas aryne 1° C--H bonds were participated in the insertion reaction. This dichotomy of the reaction is supported by the DFT calculations. Extension of this work on the sp2 C--H insertion reaction provides us a new methodology for the preparation of biaryl moieties from the alkyne building blocks. Finally, in chapter 5 we disclose conceptually distinctive method and new benzannulation reaction to generate functionalized arynes from triynes. By using this silyl substituted triynes, we prepared pharmaceutically important functionalized aryl trifluoromethylthio compounds Ar-SCF3 from aliphatic starting materials.
機(jī)譯：本文主要分為兩個(gè)部分。第一部分由兩章組成，它們描述了重氮化合物在銅催化下的銅催化反應(yīng)機(jī)理及其在點(diǎn)擊化學(xué)中的應(yīng)用。第二部分由三章組成，描述了通過過渡金屬催化反應(yīng)從多炔生成功能化芳烴的新方法。第一章包括重氮化合物與末端炔烴的銅催化反應(yīng)機(jī)理的機(jī)理研究。在這項(xiàng)工作中，借助催化劑的動(dòng)力學(xué)偏好，交叉實(shí)驗(yàn)數(shù)據(jù)和漢密特圖，我們收集了有關(guān)炔烴與乙炔銅介導(dǎo)的CH插入機(jī)理的乙炔銅與炔烴之間反應(yīng)的大量證據(jù)。重氮化合物與CuI。第2章介紹了一種新穎的三組分偶聯(lián)反應(yīng)，該反應(yīng)通過用重氮化合物原位捕獲5-銅-1,2,3-三唑中間體來制備1,4,5-三取代-1,2,3-三唑。突出顯示了選擇的實(shí)施例以說明反應(yīng)的范圍以及炔烴和疊氮化物對三組分偶聯(lián)反應(yīng)的電子作用。此方法可進(jìn)一步擴(kuò)展為一步制備融合的三唑基序。第二部分，第3章討論了基于HDDA的芳烴化學(xué)及其應(yīng)用的最新進(jìn)展的簡要調(diào)查。第4章揭示了芳烴中間體的甲硅烷基的β-碳上的CH鍵具有前所未有的雙重反應(yīng)性。在這種2°和3°C-H鍵與硅鍵僅進(jìn)行1,5-氫化物轉(zhuǎn)移，而芳烴1°C-H鍵參與插入反應(yīng)。 DFT計(jì)算支持該反應(yīng)的二分法。在sp2 CH插入反應(yīng)中這項(xiàng)工作的擴(kuò)展為我們提供了一種從炔烴結(jié)構(gòu)單元制備聯(lián)芳基部分的新方法。最后，在第5章中，我們從概念上與眾不同的方法和新的苯環(huán)化反應(yīng)公開了從三炔生成官能化的芳烴的方法。通過使用這種甲硅烷基取代的三炔，我們從脂肪族原料中制備了藥學(xué)上重要的官能化芳基三氟甲硫基化合物Ar-SCF3。

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  • 作者單位

    University of Illinois at Chicago.;

  • 授予單位 University of Illinois at Chicago.;
  • 學(xué)科 Organic chemistry.
  • 學(xué)位 Ph.D.
  • 年度 2015
  • 頁碼 319 p.
  • 總頁數(shù) 319
  • 原文格式 PDF
  • 正文語種 eng
  • 中圖分類 遙感技術(shù);
  • 關(guān)鍵詞

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