PtCl_2催化邻炔基苯胺与缺电子炔烃的串联反应研究及6，7-环氧炔的环化反应研究
摘要
本论文对铂或金催化碳碳叁键参与的反应作了一些研究。内容共分为两个部分:第一部分简要总结了近年来铂金催化的有机反应的研究进展;第二部分是我自己的硕士论文工作,分为两章:
第一章介绍了PtCl_2催化的邻炔基苯胺与缺电子炔烃的反应研究。我们利用PtCl_2催化吲哚和丙炔酸乙酯反应,得到了单加成和双加成产物。产物的组成很大程度上受吲哚上的取代基和丙炔酸乙酯的用量影响。在PtCl_2催化下,邻炔基苯胺与丙炔酸乙酯和丁炔二酸二甲酯反应生成相应的2,3-二取代吲哚,反应过程按照一个环化/分子间加成的方式进行。
第二章介绍了PtCl_2/BF_3·Et_2O和AuCl_3催化的环氧炔的分子内环化反应研究。我们发现了PtCl_2/BF_3·Et_2O和AuCl_3在甲醇中催化6,7-环氧炔能以很好的产率得到吗啉衍生物和1,4-二氧六环衍生物,这为合成吗啉衍生物和1,4-二氧六环衍生物提供了一个方便的路线。同时,我们还发现了在丙酮中回流,PtCl_2/BF_3·Et_2O能催化6,7-环氧炔,以中等产率得到一种桥环化合物。
The thesis deals with platinum and gold-catalyzed reactions which involve the activation of alkynes. It consists of two parts: In the first part, the recent progress in the area of homogenous platinum and gold catalysis is briefly reviewed with an emphasis on its synthetic applications. The second part describes our own efforts in finding synthetic applications for platinum and gold-catalyzed reactions of alkynes. We found that PtCl_2 could promote the reactions of indoles with ethyl propiolate. The composition of the products was largely influenced by the substituents on the indoles as well as the amount of ethyl propiolate used. o-Alkynylanilines could react with ethyl propiolate and dimethyl acetylenedicarboxylate under the catalysis of PtCl_2, and the reactions proceeded though a sequential cyclization/intermolecular addition pathway. Beside this work, PtCl_2 and AuCl_2-catalyzed cyclization reactions of 6,7-epoxy-alkynes were also investigated. The reactions took place in methanol or in acetone, giving rise to six-membered oxygen- containing heterocycles.
第一章介绍了PtCl_2催化的邻炔基苯胺与缺电子炔烃的反应研究。我们利用PtCl_2催化吲哚和丙炔酸乙酯反应,得到了单加成和双加成产物。产物的组成很大程度上受吲哚上的取代基和丙炔酸乙酯的用量影响。在PtCl_2催化下,邻炔基苯胺与丙炔酸乙酯和丁炔二酸二甲酯反应生成相应的2,3-二取代吲哚,反应过程按照一个环化/分子间加成的方式进行。
第二章介绍了PtCl_2/BF_3·Et_2O和AuCl_3催化的环氧炔的分子内环化反应研究。我们发现了PtCl_2/BF_3·Et_2O和AuCl_3在甲醇中催化6,7-环氧炔能以很好的产率得到吗啉衍生物和1,4-二氧六环衍生物,这为合成吗啉衍生物和1,4-二氧六环衍生物提供了一个方便的路线。同时,我们还发现了在丙酮中回流,PtCl_2/BF_3·Et_2O能催化6,7-环氧炔,以中等产率得到一种桥环化合物。
The thesis deals with platinum and gold-catalyzed reactions which involve the activation of alkynes. It consists of two parts: In the first part, the recent progress in the area of homogenous platinum and gold catalysis is briefly reviewed with an emphasis on its synthetic applications. The second part describes our own efforts in finding synthetic applications for platinum and gold-catalyzed reactions of alkynes. We found that PtCl_2 could promote the reactions of indoles with ethyl propiolate. The composition of the products was largely influenced by the substituents on the indoles as well as the amount of ethyl propiolate used. o-Alkynylanilines could react with ethyl propiolate and dimethyl acetylenedicarboxylate under the catalysis of PtCl_2, and the reactions proceeded though a sequential cyclization/intermolecular addition pathway. Beside this work, PtCl_2 and AuCl_2-catalyzed cyclization reactions of 6,7-epoxy-alkynes were also investigated. The reactions took place in methanol or in acetone, giving rise to six-membered oxygen- containing heterocycles.
引文
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