自由基型的脂肪醛与烯烃脱羰—加成反应研究

发布时间：2018-12-27 12:21

【摘要】：构筑新的化学键是有机合成化学的核心,也是合成人类所需要的医药、农药和各种有机功能材料的基础和关键。近几十年来,关于过渡金属催化的偶联反应生成新的化学键的报道也层出不穷。但是随着近些年“绿色化学”概念的兴起,发展条件温和的、环境友好的、原料易得的合成路线成为了有机合成化学研究的新方向。本论文围绕发展“环境友好的脱羰反应构筑新的化学键”这一核心主题,研究了在非金属参与的条件下,分别实现了脂肪醛与脂肪烯烃和芳香烯烃之间的脱羰-加成反应。具体研究内容包括以下两个方面:1、在无金属参与的条件下,实现了脂肪醛与缺电子烯烃之间的脱羰-加成反应。该反应以过氧化二叔丁基作为自由基引发剂和氧化剂,引发醛C(sp2)-H键均裂,转化为酰基自由基,再脱去一分子CO,形成的烷基自由基加成到烯烃的双键上,选择性的得到单一的脱羰-加成产物。该反应对于直链和支链的醛都有较好的容忍性,同时拓宽了过氧化物促进的醛类的脱羰反应的适用范围。2、发展了一种在非金属参与的条件下,以廉价的脂肪醛为原料,实现了醛、N-羟基邻苯二甲酰亚胺(NHPI)和芳香烯烃之间的三组分氧化脱羰烷基化-氨氧化反应,依次构筑C-C键和C-O键的新方法。该反应同样以过氧化二叔丁基(DTBP)为自由基引发剂和氧化剂,反应产率高,条件温和,且同时适用于末端芳香烯烃和非末端芳香烯烃,这是首次将醛的脱羰反应运用于烯烃的双官能化。同时,我们研究的目标产物非常容易去保护得到烷氧基胺化合物,因此该三组分的氧化脱羰烷基化-氨氧化反应为烷氧基胺类化合物的合成提供了一条较为新颖的方法。
[Abstract]:The construction of new chemical bonds is the core of organic synthetic chemistry and the basis and key of synthetic medicine, pesticide and all kinds of organic functional materials. In recent decades, there have been numerous reports of transition metal-catalyzed coupling reactions forming new chemical bonds. However, with the rise of the concept of "green chemistry" in recent years, the development of mild, environmentally friendly and easily available raw materials has become a new direction of organic synthesis chemistry. This paper focuses on the development of new chemical bonds for environmentally friendly decarbonylation, and studies the decarbonylation and addition of aliphatic aldehydes, aliphatic olefins and aromatic olefins under the condition of non-metallic participation. The specific research contents include the following two aspects: 1. Decarbonylation of aliphatic aldehydes and electron deficient alkenes was realized under the condition of no metal participation. In this reaction, di-tert-Ding Ji peroxide was used as a radical initiator and oxidant to initiate the splitting of C (sp2) -H bond of aldehydes, which was converted into acyl radical, and then the alkyl radical formed by a molecule of CO, was added to the double bond of olefin. A single decarbonylation-addition product was obtained selectively. This reaction has good tolerance for both straight chain and branched aldehydes, and broadens the application range of peroxide-promoted decarbonylation of aldehydes. 2. A kind of aliphatic aldehydes was developed under the condition of non-metallic participation and cheap aliphatic aldehydes as raw materials. The oxidative decarbonylation of aldehydes, N-hydroxyphthalimide (NHPI) and aromatic olefin was carried out in order to form C-C bond and C-O bond. The reaction was also carried out with di-tert-Ding Ji (DTBP) as the free radical initiator and oxidant. The reaction yield was high, the conditions were mild, and the reaction was suitable for both terminal aromatic olefins and non-terminal aromatic olefins. This is the first time that the decarbonylation of aldehydes has been applied to the difunctionalization of olefins. At the same time, the target product of our study is very easy to protect to obtain alkoxy amine compounds. Therefore, the oxidative decarbonylation of these three components provides a novel method for the synthesis of alkoxy amines.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

【相似文献】