自由基促进的Si-H键选择性官能团化构筑C-Si键的研究

发布时间：2018-06-24 11:16

本文选题：自由基化学 + 有机硅化合物　；参考：《兰州大学》2017年博士论文

【摘要】：有机硅化合物广泛存在于材料科学、药物分子及生物活性分子中。硅元素在地壳中的含量仅次于氧,然而在合成化学上,有效的构筑C-Si键的方法却并不多见。近年来,各国科学家的注意力一直集中在高效构筑C-Si键这一课题上,并取得了一系列进展。本论文首先概述了该领域的最新研究进展,其次详细介绍了本课题组发展的几类通过自由基策略,选择性官能团化硅烷中的Si-H键,高效构筑C-Si键的方法。最后对该研究领域进行了总结和展望。本文从以下四个方面展开。第一章概述了近年来在构筑C-Si键研究领域取得的进展。本章共分为两个部分,第一部分总结了通过过渡金属催化,实现C-H键硅基化的方法;第二部分,介绍了最近几年通过自由基途径构筑C-Si键的一系列进展。第二章细致论述了本课题组研究发展的一种选择性官能团化Si-H/C-H键,经自由基串联历程一步高效实现活化烯烃的硅基-芳基化的合成方法。该方法为合成硅烷取代的吲哚酮类衍生物提供了一条有效途径。第三章详细描述了本课题组研究发现的一种合成硅烷取代的苯乙烯以及苯乙炔类衍生物的有效策略。该策略采用廉价易得的α,β-不饱和羧酸与硅烷反应,经自由基加成消除途径,发生脱羧直接构建C-Si键,得到单一构型的硅基化烯烃。第四章简要阐述了我们发展的一种经单电子氧化产生三氟甲基自由基策略,实现活化烯烃的三氟甲基化-串联环化,一步高效构建三氟甲基取代的杂环化合物的方法。在论文的最后,对我们课题组发展的自由基选择性活化Si-H键、构筑C-Si键的方法进行了总结,并对该领域今后的研究进行了展望。
[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 伪, 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.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O627.41

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