基于异腈的镍催化Hetero-Pauson-Khand反应研究

发布时间：2018-05-01 14:20

本文选题：类Pauson-Khand反应 + 异腈　；参考：《青岛科技大学》2017年硕士论文

【摘要】：Pauson-Khand(PK)反应,通常是由钴、铑、钯、钼等过渡金属催化的烯、炔和一氧化碳的环加成反应,是合成环戊烯酮最有用的方法。异腈与一氧化碳互为等电子体,是一种稳定的碳烯,其参与的Hetero-Pauson-Khand(HPK)反应不但简化了反应装置,还可以合成噻吩并[2,3,b]吲哚类衍生物,且这些衍生物不仅具有良好的生物学活性,还在材料学上有一定的应用。传统的PK反应虽然具有优越的原子经济性和良好的底物适用性,但仍不可避免的存在一些局限性:如贵金属催化剂的使用量较大,产率不高,反应条件苛刻等。第一章综述了HPK型反应、镍催化的反应概述以及异腈参与的杂环化合物的合成。第二章构建了一种以邻炔基异硫氰酸酯和异腈为原料,由Ni(acac)_2催化,发生HPK反应,合成多取代噻吩并[2,3,b]吲哚类衍生物的新方法。通过条件优化,确定了以2-甲基四氢呋喃为溶剂,0.3 mol%的Ni(acac)_2为催化剂,邻炔基异硫氰酸酯:异腈=1:1.2,80 oC下反应合成噻吩并吲哚衍生物的最佳条件。底物拓展的结果表明,该方法有广泛的官能团耐受性和良好的收率。GC-MS、TEM、XPS等的检测结果以及对可能中间体的Gaussian calculation,为反应机理的推测提供了有力的支持。该方法操作简单,产率高,后处理方便,具有良好的原子经济性,且未见文献报道。所有新合成的化合物均经过IR、~1H NMR,~(13)C NMR及HRMS表征,并借助3a和3s的单晶数据,确定了目标化合物的准确结构。
[Abstract]:Pauson-Khandan (PKK) reaction, usually a cycloaddition of alkene, acetylene and carbon monoxide catalyzed by transition metals such as cobalt, rhodium, palladium, molybdenum, is the most useful method for the synthesis of cyclopentenone. Isonitrile and carbon monoxide are iso-electron bodies, and they are stable carbonene. The Hetero-Pauson-Khandon HPKK reaction not only simplifies the reaction device, but also synthesizes thiopheno [2o 3b] indole derivatives, and these derivatives not only have good biological activity, but also have good biological activity. Also has certain application in the material science. Although the traditional competitive reaction has superior atomic economy and good substrate applicability, there are still some limitations, such as large use of noble metal catalyst, low yield, harsh reaction conditions and so on. In chapter 1, HPK type reaction, nickel catalyzed reaction and synthesis of heterocyclic compounds involving isonitrile are reviewed. In chapter 2, a new method for the synthesis of polysubstituted thiopheno [2o 3nb] indole derivatives from o-alkynyl isothiocyanate and isonitrile by HPK reaction catalyzed by Ni(acac)_2 has been developed. The optimum conditions for the synthesis of thiophene indoles derivatives by reaction of o-alkylidene isothiocyanate and isonitrile 1: 1.2 ~ 80oC using 2-methyltetrahydrofuran as solvent 0.3 mol% Ni(acac)_2 as catalyst were determined. The results of substrate expansion show that the method has extensive functional group tolerance and good yield. The detection results of GC-MSX TEMX and the Gaussian calculationof possible intermediates provide strong support for the prediction of reaction mechanism. The method is simple in operation, high in yield, convenient in post-processing, and has good atomic economy, and has not been reported in literature. All the newly synthesized compounds were characterized by 1H NMR and HRMS, and the exact structure of the target compounds was determined by the single crystal data of 3a and 3s.
【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

【相似文献】