草酰胺导向下钯催化胺类C-X（杂原子）成键反应研究

发布时间：2018-01-07 02:31

本文关键词：草酰胺导向下钯催化胺类C-X（杂原子）成键反应研究　出处：《苏州大学》2016年硕士论文　论文类型：学位论文

【摘要】：过渡金属催化C-H键官能团化反应是有机合成化学研究领域的重点和热点。现其已成为构建复杂结构药物分子和天然产物地高效策略之一。因为有机分子中存在大量碳氢键,因此高位点选择性的实现碳氢键官能团化反应是这一领域研究的重点。通过导向基团实现高位点选择性是最重要的策略之一。因此寻找经济便宜、合成简单、定位活性高、易于离去或转化的导向基团成为实现C-H键活化的热点和难点。本文主要研究了Pd(OAc)2催化下草酰胺导向胺类底物的γ,δ,ε位的C-X(杂原子)成键反应。本论文的主要工作包括以下四个部分:第一部分主要对过渡金属催化C-H键氟化反应研究进展进行系统总结。第二部分主要对过渡金属催化C-H键硅化反应研究进展进行系统背景介绍。第三部分主要论述了草酰胺导向下钯催化高选择性的苄胺类化合物邻位氟化反应。本论文发展的反应对于苄胺芳环上的官能团有较高的兼容性,并且达到良好到优秀的收率。在不同条件下可以实现导向基的离去或转化。第四部分主要论述了草酰胺导向下钯催化胺类底物的邻位硅化、锗化反应。首次实现胺类的的γ-C(sp~2)-H的硅化、锗化反应。同时实现了δ-C(Sp~2)-H和γ-C(sp~3)-H的硅化反应。本论文发展的方法对不同取代基都有很好的适用性,并能实现良好到优秀的收率。原料和产物都经核磁共振氢谱、碳谱、高分辨质谱的表征,并提出了可能的反应机理。
[Abstract]:The transition metal catalyzed C-H bond functionalization reaction is a key and hot research field of organic synthesis chemistry. It has become one of the drug molecules and complex structure of natural products efficient strategy construction. Because there are a lot of C-H bond in organic molecules, so the high selective implementation of C-H functionalization reactions is the focus of the research in this field. Through oriented groups to achieve high selectivity is one of the most important strategies. So looking for cheap, simple synthesis, high positioning activity, easy oriented groups away or become hot points to realize the conversion of C-H bond activation and difficulties. This paper mainly studies Pd (OAc) gamma, oxalamide oriented amine 2 of the substrate under the catalysis. E, the C-X (hetero) bonding reaction. The main work of this thesis includes the following four parts: the first part is mainly on the research progress of the reaction of transition metal catalyzed C-H bond fluoride system The second part mainly summarized. The research progress of reaction catalyzed by transition metal silicide system C-H key background. The third part mainly discusses the oxalamide guided palladium benzylamine compounds catalyzed ortho fluorination selectivity. The reaction has high compatibility for the functional groups on the aromatic ring of benzylamine, and achieved good to excellent the yield under different conditions can be achieved. The guide base away or transformation. The fourth part mainly discusses the oxalamide under the guidance of palladium silicide catalytic amine ortho substrate, germanium gamma -C reaction. For the first time the amine (sp~2) -H silicon germanium reaction. At the same time, realized the delta -C (Sp~2) -H -C and gamma (sp~3) silicide reaction of -H. This method of development on different substituents have good applicability, and can achieve good to excellent yield. All the raw materials and the products were confirmed by 1H NMR, 13C nmr, The characterization of the high resolution mass spectrometry and the possible mechanism of the reaction were proposed.

【学位授予单位】：苏州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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