【作者】 王也铭；

【导师】 刘群；

【作者基本信息】 东北师范大学 ， 有机化学， 2011， 博士

【摘要】 随着全球生态环境的急剧恶化,人类正面临着前所未有的生存危机,如何实现可持续发展已成为人类社会面临的重大问题。近年来,以从源头上消除污染、节省资源为核心的绿色化学研究已经成为解决日益严峻的生态环境问题的强有力手段。因此,开发高效无毒、绿色环保、价格低廉的催化体系已成为当代有机化学研究的重要内容。与金、铑、钌、钯等贵金属相比,铁催化剂价格低廉、环境友好,所以铁催化的反应研究已成为当前有机化学研究的热点,铁催化的反应类型也不断地涌现,包括氧化、还原、偶联、取代、加成、环加成与环扩张、多组分反应等多种类型。本论文主要论述了利用三价铁盐作为催化剂,从α-取代-β-二羰基化合物出发,通过分子内环化反应或分子间串联反应,合成几类重要的杂环结构,包括:喹啉酮、吡咯、吡唑,以及烯胺酮类化合物,为这些化合物的制备提供新颖的合成方法。在具体的研究过程中,我们主要完成了以下工作:（1）通过对催化剂、反应溶剂、反应温度等进行反应条件优化,确定了最佳的反应条件,并且在最佳的反应条件下合成几类杂环化合物以及烯胺酮类化合物。（2）通过理论计算、捕获反应中间体等方法,研究了反应机理,初步揭示了反应规律和三价铁盐作为催化剂的作用机制。本论文共分为五章,第一、二章分别综述了近几年来铁催化有机化学反应的研究进展以及本论文的选题依据。在第三章,我们利用廉价的FeCl₃作为催化剂,从N-烷基-α,α-双烷基取代乙酰乙酰芳胺类化合物出发,实现了第一例铁催化的分子内芳环与非活化的酮羰基的烯基化反应,制备了具有抗HIV病毒活性的4-亚甲烯基-2-喹啉酮类化合物。同时,结合理论计算与实验设计,提出了可能的反应机理。在第四章,我们提出利用三价铁盐作为催化剂,从非环前体4-丁炔基酮类化合物出发,经由与伯胺的[4C+1N]型环化反应,合成多取代吡咯及吡咯并环化合物的新策略,并且提出了一种可能的反应机理。在第五章,我们利用三价铁盐作为催化剂,实现了铁催化的β-羰基-1,3-二噻烷与胺（或氨水）的胺解反应,合成了立体构型确定的β-烯胺酮类化合物。进一步,利用水合肼作为胺源合成了3,4-二取代吡唑类化合物。更多还原

【Abstract】 With a sharp deterioration in the global ecological environment, human beings are facing an unprecedented crisis of survival, how to achieve sustainable development have become major problems. In recent years, in order to eliminate the pollution from the source, saving resources as the core of green chemistry research has become to solve the increasingly serious environmental problems of the powerful tool. Therefore, the development of efficient non-toxic, green, inexpensive catalyst system has become an important part of modern organic chemistry research. Compared with gold, rhodium, ruthenium, palladium and other precious metals, iron catalyst are inexpensive, environmentally friendly, so the iron-catalyzed reaction has become a hot research in organic chemistry. And the typies of reactions catalyzed by iron salts also continue to emerge, including oxidation, reduction , coupling, replacement, addition, cycloaddition and ring extensions, multicomponent reactions, and so on.This dissertation mainly discusses using iron（Ⅲ） salts as catalysts, several important application classes of heterocyclic compounds, including quinolinones, pyrroles, pyrazoles and enamintones are synthesized based on theα-substituted-β-dicarbonyl compounds by intramolecular cyclization or intermolecular tandem reaction. In the specific research process, we mainly have completed the following major tasks:（1） we determined the optimizing conditions through screening of reaction conditions like the catalyst, solvent, reaction temperature and so on, and synthesized several series heterocyclic compounds and enamintones under optimal conditions.（2） We studied the reaction mechanism in-depth by theoretical calculations and capturing reaction intermediates, so that we understood the reaction rules and the important role of iron（Ⅲ） salts as catalysts.This dissertation is divided into five chapters. The first chapter introduce reviews the development of research on iron catalysts in recent years. And the dissertation proposal was presented in the second chapter.The third chapter, we fistly realized the intramolecular aromatic C-H alkenylation of arenes with non-activated ketones to synthesize 4-alkenylquinolin-2-ones prosessing anti-HIV activities by using FeCl₃ as a catalyst and N-alkyl-α,α-dialkyl substituted acetoacetarylamides as starting materials. According to theoretical calculations and experimental plans, the possible reaction mechanism is proposed.The fourth chapter shows a novel strategy for the synthesis of polysubstituted pyrroles via[4C+1N] cyclization of 4-acetylenic ketones with primary amines by using the iron（III） salt as a catalyst. And the possible reaction mechanism is proposed.The fifth chapter briefly involves iron（Ⅲ） salts-catalyzed aminalysis ofβ-carbonyl 1,3-dithianes to synthesize stereodefined enaminones and 3,4-disubstituted pyrazoles.更多还原