XJIPC OpenIR  > 资源化学研究室
Thesis Advisor卢崇道
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline有机化学
KeywordN-(9-呫吨基)-4-甲基苯磺酰胺 水杨醛亚胺 苯炔 加成-环化 串联反应
Other Abstract

苯炔是一类重要的有机反应中间体,因其具有极高的反应活性而受到重视。自温和条件下高效地产生苯炔的方法发现以来,有关苯炔参与的有机反应在合成上的应用得到了长足发展。苯炔在有机合成中制备1,2 二取代的芳烃化合物和其他一些包含芳基的化合物方面有着广泛的应用。

本论文研究了以邻(三甲基硅基)芳基三氟甲磺酸酯类化合物作为苯炔前体,经过氟离子引发苯炔的产生,并与水杨醛磺酰亚胺发生亲核加成-环合串联反应,合成N-9-呫吨基)-4-甲苯磺酰胺类化合物的合成方法。该反应一步形成CO CC两个化学键,反应条件温和、产率高,且具有良好的底物延展性和官能团耐受性,为合成C-9 位氨基氧杂蒽分子骨架的有机化合物提供了一种温和的、简便有效的合成路径。在上述研究基础上,本论文同时研究了苯炔与手性亚胺(N-叔丁基亚磺酰胺与4-溴代水杨醛缩合而成)的反应,希望通过手性基团的引入,实现反应的立体控制。实验结果表明该反应在CsF-CH3CN 体系中总产率可达89%,但产物的非对映选择性

稍差(d.r. = 1.4:1)。

As important intermediates in organic reacton, arynes have attracted a great deal of attention owing to their highly reactive property. Since the milder preparation of benzynes was developed, it has made considerable progress on numerous reactions and applications in organic synthesis. Arynes are widely used in organic transformation to construct 1,2-disubstituted arenes and other useful compounds containing aryl groups. The thesis explores the addition-cyclization cascade reaction of salicyl N-tosylimines with arynes, which are formed from silylaryl triflates in the presence of fluorion. The cas-cade reaction provides a mild and efficient method for facile synthesis of N-(9-xanthyl)-4-toluenesulfonamides. In addition, the cascade promote the formation of C-O and C-C bonds in one step, and the mild conditions are compatible with a variety of functional groups in this high yield reaction. We have developed a mild and efficient entry point into the synthesis of 9-amine xanthenes. Based on the aforementioned studies, the reaction of benzynes with the chiral imine (N-tert-butyl sulfonamide with 4-bromo-salicyladehyde in a condensation reaction) was explored. We hope to get a good stereoselectivity in this reaction by using the chiral group. As a result, the experiments show that the overall yield is 89% in CsF-CH3CN system, however, the diastereoselectivity of product is poor (d.r. = 1.4:1). Key Words: N-(9-xanthyl)-4-toluenesulfonamides, salicyl N-tosylimines, arynes, addition-cyclization, cascade.
Document Type学位论文
Recommended Citation
GB/T 7714
芦珊珊. 苯炔与水杨醛亚胺的加成-环化串联反应研究[D]. 北京. 中国科学院大学,2013.
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