双核锌催化剂催化α-羟基苯乙酮的不对称耦合反应的研究

发布时间：2018-01-13 17:37

本文关键词：双核锌催化剂催化α-羟基苯乙酮的不对称耦合反应的研究　出处：《郑州大学》2017年硕士论文　论文类型：学位论文

【摘要】：手性2,3-二羟基-1,4-二酮中间体具有重要的应用价值,不仅广泛存在天然产物及药物活性分子中,而且其进一步衍生得到的产物TADDOL((4S,5S)-2,2-二甲基-a,a,a',a'-四苯基-1,3-二氧戊环-4,5-二甲醇)可以作为不对称反应的催化剂。通过调研文献发现,有关2,3-二羟基-1,4-二酮化合物的合成报道甚少,而且主要是以副产物的形式出现。这些已报道的合成方法不仅步骤复杂,产率低,而且得到的产物都是非手性的,采用不对称催化手段合成此类手性化合物的报道几乎没有。因此,通过简单高效的不对称催化手段来合成手性2,3-二羟基-1,4-二酮化合物具有重要的医药和科研价值。本文的主要研究内容是利用不对称催化的新方法来合成手性2,3-二羟基-1,4-二酮化合物,即在双核锌催化剂作用下对苯二醌氧化α-羟基苯乙酮生成苯甲酰甲醛,再与α-羟基苯乙酮发生不对称Aldol反应,得到目标产物,反应的对映选择性高达ee=97%,非对映选择性高达dr=19:1。
[Abstract]:Chiral intermediates of 2O3-dihydroxy-1-diketone have important application value, not only exist in natural products and drug active molecules. Furthermore, the product of TADDOLX 4S ~ (5) S ~ (5) S ~ (2) O ~ (2) ~ (2) -dimethyl ~ (2) -a ~ (1) -diphenyl ~ (-1) ~ (3) -dioxolane ~ (4) was obtained by further derivation of the product. 5-dimethyl alcohol) can be used as a catalyst for asymmetric reactions. It is found that there are few reports on the synthesis of 2O3-dihydroxy-1-diketone compounds. These reported synthesis methods are not only complex steps, low yield, but also the products are non-chiral. There are few reports on the synthesis of such chiral compounds by asymmetric catalysis. Therefore, chiral 2o 3-dihydroxy-1 is synthesized by a simple and efficient asymmetric catalytic method. 4-diketone compounds are of great value in medicine and scientific research. In this paper, a new method of asymmetric catalysis is used to synthesize chiral 2O3-dihydroxy-1-diketone compounds. In the presence of binuclear zinc catalyst, p-phenylquinone oxidized 伪 -hydroxyacetophenone to form benzoyl formaldehyde, and then asymmetric Aldol reaction with 伪 -hydroxyacetophenone was carried out to obtain the target product. The enantioselectivity of the reaction is as high as Eee 97 and the enantioselectivity up to 19: 1.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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