氮杂环卡宾催化α,β-不饱和醛的硫基化反应研究
发布时间：2019-06-30 21:30
【摘要】：硫基化反应是有机合成中一种重要的化学反应,能够有效的构筑碳-硫键。近些年来,化学家们对硫基化反应研究已经取得了显著的成果,主要集中在有机小分子催化或过渡金属催化构建sp~3碳-硫键,而构建sp~2碳-硫键大多是通过过渡金属催化卤代芳烃、卤代烯烃的交叉偶联反应或者炔烃的加成反应得到,但大部分过渡金属价格昂贵、毒性较大。因此,发展绿色、经济、环境友好的构建sp~2碳-硫键的方法有着重要意义。本论文主要包含三章内容:第一章综述了有机小分子催化的亲电硫试剂参与构筑碳-硫键的反应研究进展。主要包括不对称硫基化反应、不对称硫胺化反应、不对称硫醚化反应等,为合成高对映选择性的有机硫化合物提供了有效途径。第二章主要介绍了氮杂环卡宾催化α,β-不饱和醛的硫基化反应研究。我们发展了首个氮杂环卡宾催化的α,β-不饱和醛与N-芳硫基邻苯二甲酰亚胺的硫基化反应,有效的保留了醛基,为sp~2碳-硫键的形成提供了一种绿色、高效的新方法。该方法有良好的兼容性,各类底物均能达到较高的产率以及良好的Z/E选择性。第三章主要研究了氮杂环卡宾催化烯酮与亚胺的环加成反应。我们设想使用手性氮杂环卡宾催化烯酮与亚胺醌环加成再异构化,得到手性吲哚酮类化合物。经过初步尝试,我们已得到了目标产物,但立体选择性控制不太理想,之后,我们将进一步尝试。
[Abstract]:Thiomerization is an important chemical reaction in organic synthesis, which can effectively construct carbon-sulfur bond. In recent years, chemists have made remarkable achievements in the study of sulfur reaction, mainly focusing on the construction of sp~3 carbon-sulfur bond catalyzed by small organic molecules or transition metals. The construction of sp~2 carbon-sulfur bond is mostly obtained by transition metal catalyzed halogenated aromatics, cross-coupling reaction of halogenated alkenes or addition of alkynes, but most of the transition metals are expensive and toxic. Therefore, it is of great significance to develop green, economic and environmentally friendly methods to construct sp~2 carbon-sulfur bond. The main contents of this paper are as follows: in the first chapter, the research progress of organic small molecule catalyzed electrophilic sulfur reagents in the construction of carbon-sulfur bond is reviewed. It mainly includes asymmetric thiomerization reaction, asymmetric thiamine reaction, asymmetric thioetherification reaction and so on, which provides an effective way for the synthesis of organic sulfur compounds with high enantioselectivity. In the second chapter, the thiomerization of 伪, 尾-unsaturated aldehydes catalyzed by azacyclocarbene is introduced. We have developed the first thiomerization reaction of 伪, 尾-unsaturated aldehyde with N-arylthio phthalimide catalyzed by azacyclocarbene, which effectively preserves aldehyde group and provides a new green and efficient method for the formation of carbon-sulfur bond in sp~2. This method has good compatibility, and all kinds of substrate can achieve high yield and good Z / E selectivity. In the third chapter, the cycloaddition reaction of ketene with imine catalyzed by azacyclocarbene was studied. We imagine using chiral azacyclocarbene to catalyze the addition and re-isomerization of enolones with imine quinones to obtain chiral indolones. After a preliminary attempt, we have obtained the target product, but the stereoselective control is not ideal, and then we will try further.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
[Abstract]:Thiomerization is an important chemical reaction in organic synthesis, which can effectively construct carbon-sulfur bond. In recent years, chemists have made remarkable achievements in the study of sulfur reaction, mainly focusing on the construction of sp~3 carbon-sulfur bond catalyzed by small organic molecules or transition metals. The construction of sp~2 carbon-sulfur bond is mostly obtained by transition metal catalyzed halogenated aromatics, cross-coupling reaction of halogenated alkenes or addition of alkynes, but most of the transition metals are expensive and toxic. Therefore, it is of great significance to develop green, economic and environmentally friendly methods to construct sp~2 carbon-sulfur bond. The main contents of this paper are as follows: in the first chapter, the research progress of organic small molecule catalyzed electrophilic sulfur reagents in the construction of carbon-sulfur bond is reviewed. It mainly includes asymmetric thiomerization reaction, asymmetric thiamine reaction, asymmetric thioetherification reaction and so on, which provides an effective way for the synthesis of organic sulfur compounds with high enantioselectivity. In the second chapter, the thiomerization of 伪, 尾-unsaturated aldehydes catalyzed by azacyclocarbene is introduced. We have developed the first thiomerization reaction of 伪, 尾-unsaturated aldehyde with N-arylthio phthalimide catalyzed by azacyclocarbene, which effectively preserves aldehyde group and provides a new green and efficient method for the formation of carbon-sulfur bond in sp~2. This method has good compatibility, and all kinds of substrate can achieve high yield and good Z / E selectivity. In the third chapter, the cycloaddition reaction of ketene with imine catalyzed by azacyclocarbene was studied. We imagine using chiral azacyclocarbene to catalyze the addition and re-isomerization of enolones with imine quinones to obtain chiral indolones. After a preliminary attempt, we have obtained the target product, but the stereoselective control is not ideal, and then we will try further.
【学位授予单位】：西北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
【相似文献】
相关期刊论文 前10条
1 蒋锡夔;;卡宾的化学[J];化学通报;1962年07期
2 蒋锡夔;;卡宾化学的进展及某些问题[J];科学通报;1965年08期
3 张必良;;卡宾化学分支——高张力环卡宾的进展[J];化学通报;1987年11期
4 马艳凤,马楠,孟繁友;关于卡宾的研究[J];松辽学刊(自然科学版);1997年03期
5 孙小宇;吴R，
本文编号：2508271
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2508271.html
教材专著
