新型催化剂的合成及其在不对称Michael加成反应中的应用

发布时间：2018-01-30 00:06

本文关键词： 二茂铁胺-硫脲催化剂 Michael加成反应硝基烯烃乙酰丙酮　出处：《第四军医大学》2014年硕士论文　论文类型：学位论文

【摘要】：最近十多年，双功能的胺-硫脲类有机小分子催化剂在不对称催化反应方面有了很大的发展。经典的双功能胺-硫脲类催化剂主要有衍生于环己二胺或1,2-二胺的、金鸡纳碱的、联萘二胺等的衍生物。二茂铁因其刚性强、易衍生、结晶性好、稳定等优点一直被作为金属催化中配体的优势骨架，，然而却一直没有被用作构建有机小分子催化剂的骨架。本课题首次以二茂铁为骨架，设计合成了新型的基于二茂铁的双功能胺-硫脲类催化剂，其分子中两个不同官能团同时并独立地活化亲核和亲电底物以及在优良的手性环境中控制不对称诱导，从而达到不对称催化的目的。论文的主要内容有以下两个方面： 1.设计并以Ugi’s胺、对甲苯磺酰氯、叠氮钠和异硫氰酸酯等为原料合成了一种以二茂铁为骨架的新型双功能胺-硫脲类催化剂，催化剂的结构通过1H NMR、13C NMR、HRMS等图谱数据的确证。 2.初步探索了基于二茂铁的新型双功能胺-硫脲类催化剂在硝基烯烃类化合物与乙酰丙酮的不对称Michael加成反应中的催化效果。在10mmol%催化剂83催化下，以甲苯为溶剂，常温下反应60h可以得到较高的产率和最高达96%ee的对映选择性，而且产物的优势构型为R构型。实验结果证明,我们所设计合成的以二茂铁为骨架的新型双功能胺-硫脲类催化剂在硝基烯烃类化合物与乙酰丙酮的不对称Michael加成反应中表现出非常好的催化效果，可以得到最高达96%ee的对映选择性。这一结果表明，与金属催化剂一样，二茂铁也是有机小分子催化剂的优秀骨架。
[Abstract]:The last more than 10 years, bifunctional amine thiourea organocatalysts has made great progress in asymmetric catalysis. The classical bifunctional amine thiourea catalysts are mainly derived from Cyclohexanediamine or 1,2- two amine, Cinchona, binaphthyl two amine derivatives. Two ferrocene because of its strong rigidity, easy derivatization, good crystallization, high stability and has been used as a ligand in catalytic metal skeleton advantage, but it has not been used for construction of organic small molecule catalyst skeleton.
This is the first study to two ferrocene skeleton, bifunctional amine two ferrocene based on thiourea catalysts synthesized a new design, the two different functional groups simultaneously and independently activated nucleophilic and electrophilic substrates and control of asymmetric induction in excellent chiral environment, so as to achieve the purpose of asymmetric catalysis. The main content of the thesis includes the following two aspects:
1., we designed a new bifunctional amine thiourea catalyst based on Ugi 's amine, toluene sulfonyl chloride, sodium azide and isothiocyanate as raw materials. The structure of the catalyst was confirmed by 1H NMR, 13C NMR, HRMS and other map data. Two.
2. preliminary exploration of two ferrocene new bifunctional amine thiourea catalysts in asymmetric Michael nitro olefin compounds with acetylacetone addition reaction. Based on the catalytic effect of 10mmol% catalyst in 83 catalyst, toluene as solvent, the reaction temperature of 60H can get high yield and enantioselectivity up to 96%ee, and the advantage of configuration of the product to the R configuration.
Experimental results show that, we designed and synthesized two ferrocene skeleton new bifunctional amine thiourea catalysts in asymmetric Michael nitro olefin compounds with acetylacetone addition reactions exhibit catalytic effect is very good, can get up to 96%ee EE. The results show that the same with the metal catalyst, excellent two ferrocene skeleton is organic catalysts.

【学位授予单位】：第四军医大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914

【共引文献】