本文選題：自由基化學(xué) + 有機(jī)硅化合物　； 參考：《蘭州大學(xué)》2017年博士論文

【摘要】：有機(jī)硅化合物廣泛存在于材料科學(xué)、藥物分子及生物活性分子中。硅元素在地殼中的含量?jī)H次于氧,然而在合成化學(xué)上,有效的構(gòu)筑C-Si鍵的方法卻并不多見(jiàn)。近年來(lái),各國(guó)科學(xué)家的注意力一直集中在高效構(gòu)筑C-Si鍵這一課題上,并取得了一系列進(jìn)展。本論文首先概述了該領(lǐng)域的最新研究進(jìn)展,其次詳細(xì)介紹了本課題組發(fā)展的幾類通過(guò)自由基策略,選擇性官能團(tuán)化硅烷中的Si-H鍵,高效構(gòu)筑C-Si鍵的方法。最后對(duì)該研究領(lǐng)域進(jìn)行了總結(jié)和展望。本文從以下四個(gè)方面展開(kāi)。第一章概述了近年來(lái)在構(gòu)筑C-Si鍵研究領(lǐng)域取得的進(jìn)展。本章共分為兩個(gè)部分,第一部分總結(jié)了通過(guò)過(guò)渡金屬催化,實(shí)現(xiàn)C-H鍵硅基化的方法;第二部分,介紹了最近幾年通過(guò)自由基途徑構(gòu)筑C-Si鍵的一系列進(jìn)展。第二章細(xì)致論述了本課題組研究發(fā)展的一種選擇性官能團(tuán)化Si-H/C-H鍵,經(jīng)自由基串聯(lián)歷程一步高效實(shí)現(xiàn)活化烯烴的硅基-芳基化的合成方法。該方法為合成硅烷取代的吲哚酮類衍生物提供了一條有效途徑。第三章詳細(xì)描述了本課題組研究發(fā)現(xiàn)的一種合成硅烷取代的苯乙烯以及苯乙炔類衍生物的有效策略。該策略采用廉價(jià)易得的α,β-不飽和羧酸與硅烷反應(yīng),經(jīng)自由基加成消除途徑,發(fā)生脫羧直接構(gòu)建C-Si鍵,得到單一構(gòu)型的硅基化烯烴。第四章簡(jiǎn)要闡述了我們發(fā)展的一種經(jīng)單電子氧化產(chǎn)生三氟甲基自由基策略,實(shí)現(xiàn)活化烯烴的三氟甲基化-串聯(lián)環(huán)化,一步高效構(gòu)建三氟甲基取代的雜環(huán)化合物的方法。在論文的最后,對(duì)我們課題組發(fā)展的自由基選擇性活化Si-H鍵、構(gòu)筑C-Si鍵的方法進(jìn)行了總結(jié),并對(duì)該領(lǐng)域今后的研究進(jìn)行了展望。
[Abstract]:Silicone compounds are widely found in materials science, drug molecules and bioactive molecules. The content of silicon in the crust is second only to that of oxygen. However, in synthetic chemistry, there are few effective methods to construct C-Si bond. In recent years, scientists all over the world have been focusing on the efficient construction of C-Si bond, and have made a series of progress. In this paper, the latest research progress in this field is first summarized, and then several methods of constructing C-Si bond by free radical strategy, selective functional group and Si-H bond in silane are introduced in detail. Finally, the research field is summarized and prospected. This article starts from the following four aspects. In the first chapter, the progress in the field of C-Si bond construction is summarized. This chapter is divided into two parts. In the first part, the methods of C-H bond silicylation by transition metal catalysis are summarized. In the second part, a series of progress in the construction of C-Si bond by free radical in recent years is introduced. In the second chapter, we discuss a kind of selective functional group Si-HrC-H bond, which can efficiently realize the silico-arylation of activated olefin by a series of free radical in one step. This method provides an effective way for the synthesis of silane substituted indole ketones derivatives. In chapter 3, we describe in detail an effective strategy for the synthesis of silane substituted styrene and phenylacetylene derivatives. In this strategy, the 偽, 尾 -unsaturated carboxylic acid can react with silane, and decarboxylation occurs to form C-Si bond directly through free radical addition elimination, and a single configuration of silicon-based olefins can be obtained. In chapter 4, we briefly describe a new method to produce trifluoromethyl radical by single electron oxidation, realize trifluoromethylation of activated olefin in series, and construct trifluoromethyl substituted heterocyclic compounds in one step. At the end of the paper, the methods of free radical selective activation of Si-H bond and C-Si bond are summarized, and the future research in this field is prospected.
【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O627.41

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