酮羰基取代的联烯三元环的区域选择性亲核加成及应用

发布时间：2018-08-20 12:30

【摘要】：联烯是一类高活性的有机分子,它作为一种重要有机合成砌块在现代有机合成中具有高度的应用价值。联烯的亲核加成反应是一类极其重要的有机反应,但由于联烯反应位点众多,在亲核加成时需要控制位点才能得到选择性好的产物。在联烯端位引入官能团能有效改变其电子云分布,当联烯与吸电子官能团相连时,就能使中间碳电子云密度降低,更倾向于发生各种亲核加成反应。本论文是基于环丙基联烯酮具有多个反应位点,利用不同类型的亲核试剂与其反应,高度区域和立体选择性地构建各种复杂分子。论文主要内容包括以下几个方面:第一部分研究了以亚磺酸钠衍生物作为亲核试剂对环丙基联烯酮的亲核加成。我们发现在不同的溶剂可以控制生成不同位点的加成产物,在MeOH中得到β-磺酰化产物,在DMSO中得到γ-磺酰化产物,两种类型磺酰化产率很高,而且立体选择性也很好,同时该反应的机理也被详细研究。接着我们对β-加成产进行碘环化得到四取代呋喃产物,同时也开发了一锅法从环丙基联烯酮与苯亚磺酸钠反应完后直接碘环化得到四取代呋喃产物,及对生成的碘代四取代呋喃产物转化研究。第二部分研究了以亚硝酸钠作为亲核试剂与环丙基联烯酮反应,同样在不同溶剂下分别得到了β,γ-二硝化,γ-硝化及分子内氧化生成肟的产物。在CH3CN作溶剂下生成β,γ-二硝化产物;在DMSO作溶剂下γ-硝化产物被得到;在CH3OH溶剂中,β,γ-二硝化产物能发生分子内氧化反应生成肟的产物。
[Abstract]:Diene is a class of highly active organic molecules. As an important organic synthetic block, it has high application value in modern organic synthesis. The nucleophilic addition reaction of diene is a very important organic reaction, but because there are many sites in the reaction, it is necessary to control the site in order to obtain the selective product. The introduction of functional groups to the terminal of bienes can effectively change the distribution of electron clouds. When they are connected with the electron functional groups, the density of intermediate carbon electron clouds can be reduced, and they tend to occur various nucleophilic addition reactions. Based on the multiple reaction sites of cyclopropyldienone, various complex molecules were constructed by using different nucleophilic reagents in high region and stereoselectivity. The main contents of this paper are as follows: in the first part, the nucleophilic addition of cyclopropylenone with sodium sulfonate derivatives as nucleophilic reagent was studied. We found that the addition products at different sites can be controlled in different solvents, 尾 -sulfonylation products can be obtained in MeOH and 纬 -sulfonylation products can be obtained in DMSO, the yields of two types of sulfonylation are very high, and the stereoselectivity is very good. At the same time, the mechanism of the reaction has also been studied in detail. Then we cyclized the 尾 -adduct to get tetrasubstituted furan products. At the same time, we also developed a one-pot method to obtain tetrasubstituted furan products from cyclization of cyclopropylenone with sodium benzenesulfonate by direct iodine cyclization. And study on the transformation of the product of tetra-substituted furan. In the second part, the products of 尾, 纬 -dinitrification, 纬 -nitration and intramolecular oxidation to form oxime were obtained by reaction of sodium nitrite with cyclopropyldienone in different solvents. 尾, 纬 -dinitrification products were obtained in CH3CN solvent; 纬 -nitration products were obtained in DMSO solvent; in CH3OH solvent, 尾, 纬 -dinitrification products could undergo intramolecular oxidation to produce oxime.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.256.7

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