N原子导向下钯催化C-H键官能团化反应研究

发布时间：2018-09-12 19:52

【摘要】：过渡金属催化的C-H键官能团反应,因为其有着原子利用率高和步骤经济性,能够快速的构筑C-C键和C-X键(X=N, O, S, Cl, I, Br等),已经应用于合成各种结构相似的天然产物和药物分子中。本论文首先概述了N原子导向下钯催化的C-H键活化反应,这类反应具有较高的区域选择性和转化率。常见的导向基团有吡啶基、乙酰基、乙酰氨基、羧酸基、乙腈基、酮基、偶氮基等,尽管这些导向基导向的C-H键活化反应的报道已有很多,但是都有着其局限性,要想使C-H键官能团化更好的应用于有机合成化学,更多C-H官能团化反应组合类型还需要我们去探究。氧化偶氮苯被广泛的用于液晶、染料和记忆材料中,其合成也备受关注,氧化偶氮苯有两个导向基团,可以和钯配位形成两种不同的金属中间体,选择性的形成单一中间体是一个挑战。我们选用氧化偶氮苯作为底物,醋酸钯作为催化剂,醋酸碘苯作为终端氧化剂,实现了高选择性,高产率的氧化偶氮苯邻位的乙酰氧化和烷氧化反应,得到了一系列的不对称氧化偶氮苯,该方法提供了一种简便、绿色合成不对称氧化偶氮苯的新途径。此外,我们发现N-亚硝基导向的C-H键官能团化报道并不多,芳基酮结构广泛的存在于天然产物中,并有着良好的生物活性。由此,我们选择亚硝基苯胺为底物,三氟乙酸钯作为催化剂,过二硫酸钾为终端氧化剂,在其邻位引入了苯甲酰基,得到了一系列芳基酮产物。之前,关于N-亚硝基导向的C-H键官能团化反应多为亚硝基断掉的例子,而该方法的亚硝基却得到了完整保留,并可以简便高效的转化为吲唑类化合物。
[Abstract]:Transition metal-catalyzed C-H bond functional group reactions, due to their high atomic utilization and step economy, It can rapidly construct C-C bond and C-X bond (XN, O, S, Cl, I, Br, etc.), and has been used in the synthesis of various natural products and drug molecules with similar structure. In this paper, the palladium catalyzed C-H bond activation reactions under N-atom guidance are reviewed. These reactions have high regioselectivity and conversion. The common targeting groups are pyridyl, acetyl amino, carboxylic acid, acetonitrile, ketone, azo and so on. In order to make C-H bond functional group better applied to organic synthesis chemistry, more C-H functionalization reaction combination types need to be explored. Oxyazobenzene is widely used in liquid crystal, dyes and memory materials, and its synthesis has attracted much attention. Oxidized azobenzene has two guiding groups, which can coordinate with palladium to form two different metal intermediates. The selective formation of a single intermediate is a challenge. Oxidation of azobenzene as substrate, palladium acetate as catalyst, iodobenzene acetate as terminal oxidant, high selectivity and high yield oxidation of azobenzene ortho acetyl and alkane were achieved. A series of asymmetric oxidized azobenzene have been obtained. This method provides a new way of green synthesis of asymmetric oxidation of azobenzene. In addition, we found that there are few reports of N-nitroso-oriented C-H bond functionalization, aryl ketones are widely present in natural products and have good biological activity. Therefore, a series of aryl ketones were obtained by using nitroso aniline as substrate, palladium trifluoroacetate as catalyst and potassium persulfate as terminal oxidant. Previously, the N-nitro-oriented C-H bond functionalization reaction was mostly nitroso broken, but the nitrosos of the method were completely retained and could be easily and efficiently converted to indazole compounds.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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