镍催化下酯的脱羰硼、硅化反应研究

发布时间：2018-03-30 07:50

本文选题：镍催化　切入点：硼基化　出处：《南京大学》2017年硕士论文

【摘要】：酯广泛存在于有机分子中,药物,农用化学品,和有机材料都含有酯基。酯的选择性官能团化在有机化学领域具有很大的挑战性。我们成功实现了酚酯在镍催化下直接脱羰基后硼基化和硅基化反应。具体结果如下所列:(1)我们发展了镍催化下,酯和双(新戊二醇)二硼(B2(nep)2)的脱羰基硼化反应,一步生成芳基硼酸酯。而要完成这个转化的关键是需要一个合适的配体以及添加剂。我们发现这个反应有着很好的官能团兼容性,可以作为将含有酚酯基团的复杂分子官能团化的有力手段。并且在此反应中,我们成功分离出两个重要的有机镍中间体,并且用单晶衍射对其结构进行表征,很有力地证明了该反应的机理。(2)我们发展了镍/铜共催化,酯和硅硼试剂(BpinSiEt3)的脱羰基硅基化反应,一步生成芳基硅烷。在这个反应过程中铜是必不可少,用来活化硅硼试剂,形成中间体(Cu-SiEt3)物种。该反应有很好的官能团兼容性,可以以良好到优异的产率得到相应的芳基硅化物。根据之前酯的脱羰基硼化反应机理研究结果,我们对酯的硅基化反应的机理也进行了推测。
[Abstract]:Esters are widely found in organic molecules, drugs, agrochemicals, The selective functional groups of esters are very challenging in the field of organic chemistry. We have successfully realized the boronylation and silicylation of phenol esters after direct decarbonylation under the catalysis of nickel. We developed a nickel catalyst, The decarbonylation reaction of ester with bis (neopentanediol) diboron B _ 2 / nep _ 2), The key to this transition is a suitable ligand and an additive. We found that the reaction had good functional compatibility. In this reaction, two important organic nickel intermediates were successfully isolated and characterized by single crystal diffraction. We have developed nickel / copper co-catalysis, the decarbonylation of esters with borosilyl reagent BpinSiEt3) to produce aryl silane in one step. Copper is essential in this process to activate silicon-boron reagents. A species of intermediate, Cu-SiEt3) was formed. The reaction has good functional compatibility, and the aryl silicides can be obtained in good to excellent yields. We also speculated on the mechanism of the silicylation of ester.
【学位授予单位】：南京大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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