Synthesis and application of tetraphenylene derivatives in asymmetric catalysis: &, Iron-catalyzed cross-coupling of organolithium compounds with organic halides

Ph.D.This thesis includes two parts. The first part described our preliminary attempt: introducing the asymmetric tetraphenylene derivatives into hetero-Diels-Alder reaction as hydrogen bonding donor catalysts.Chapter 1 gives a general review on the background of tetraphenylene involving the introduction of the unique saddle-shaped structure and preparation methods.In Chapter 2, types of asymmetric organocatalysis are briefly introduced. Here, the concept of hydrogen bonding catalysis is introduced. Recent development in this field is also reviewed especially for the bifunctional hydrogen bonding type catalysis.In Chapter 3, referring to the structures of BINOL and TADDOL, a series of asymmetric tetraphenylene derivatives 48, 182-184 and 190 were designed and synthesized. However, none of them worked well in the model reaction test presumably due to issues of solubility, acidity or steric hindrance, respectively. To our disappointment, various fluorine-substituted species 209-211 were not obtained presumably due to the decreased nucleophilicity issue.In the process of optimization of the preparation method of tetraphenylene, a novel reaction was developed, which was discussed in detail in the second part of this thesis.Chapter 4 and Chapter 5 summarize the recent development on iron-catalyzed cross-coupling reactions of Grignard reagents and palladium-catalyzed cross-coupling reactions of organolithium compounds. Our research was just based on these two classical reactions, adopting their advantages and combining them together.Chapter 6 presents specific iron-catalyzed cross-coupling reactions of organic halides with organolithium reagents. Two catalytic systems are described involving the optimization of the model reaction, the expansion of substrates scope, gram scale experiments as well as mechanism consideration.In Chapter 7, a short summary and conclusion are given.In Chapter 8, experimental details are given.論文分為兩部份。第一部份講述了我們初步的嘗試：非對稱的四苯并環辛四烯衍生物作為氫鍵供體催化劑應用於雜蒂爾斯-阿德爾反應。第一章概要地介紹了四苯并環辛四烯的背景知識，包括其獨特的馬鞍形結構及其合成方法。第二章概要地回顧了不同種類的有機非對稱催化劑。同時介紹了氫鍵催化的概念及發展近況。在第三章中，參考BINOL 和TADDOL兩種催化劑的結構特徵，我們設計并合成了一系列非對稱的四苯并環辛四烯衍生物48, 182-184及190。然而，或許是因為溶解性、酸性及空間位阻的影響，她們在模型反應中的應用並不理想。並且，或許是因為親核性降低的緣故，其相應的多種氟取代的分子209-211不能夠成功合成。論文的第二部份講述了在我們對四苯并環辛四烯合成方法的優化過程中，發現的一類新穎的反應。第四章和第五章分別總結了：鐵催化下的格式試劑參與的交叉偶聯反應，以及鈀催化下的鋰試劑參與的交叉偶聯反應。我們的研究正式基於這兩種典型的反應：我們吸取它們的優點并把它們整合在一起。第六章詳細講述了鐵催化下的鋰試劑參與的交叉偶聯反應。介紹了我們發展的兩種催化體系，包括模型反應的優化、底物拓展、放大到克級的反應以及關於反應機理的探索。第七章是總結和結論。第八章是實驗部份。Liu, Qiang.Thesis Ph.D. Chinese University of Hong Kong 2017.Includes bibliographical references (leaves 175-186).Abstracts also in Chinese.Title from PDF title page (viewed on …)