高价碘试剂介导的选择性芳香碳—氢键官能团化反应

发布时间：2018-05-26 22:21

  本文选题：高价碘试剂 + 胺化　； 参考：《湖北工业大学》2017年硕士论文

【摘要】：本文的主要内容是高价碘试剂介导的选择性芳香碳-氢键官能团化反应,分别为8-酰胺基喹啉与苯胺的5位或对位胺化反应及磺酰化反应。在高价碘试剂的介导下,无需金属催化剂或其他添加剂参与反应,即可以成功的发生胺化和磺酰化反应,具体内容如下:1.在高价碘试剂特戊酸碘苯的介导下,8-酰胺基喹啉或苯胺与N-氟代双苯磺酰胺(NFSI)发生氧化碳-氢键胺化反应,得到产率中等至较好的5位或对位的胺化产物。该反应条件温和,具有较高的区域选择性以及较好的官能团兼容性,反应不需要金属催化剂或其他氧化剂、添加剂的参与,并且能够在敞开体系下完成。该方法为制备芳胺类化合物提供了一个高效的、新颖的方法(Scheme 1)。Scheme 12.在上一个研究成果的基础上,继续探究高价碘试剂介导的碳-氢键官能团化反应体系的适用范围。实验结果发现,用磺酰氯替换NFSI后,利用该方法也可以得到8-酰胺基喹啉以及苯胺的5位或对位的磺酰化产物。在磺酰化反应中,该方法同样具有较高的区域选择性,同时对酰胺类底物以及磺酰化试剂都有较好的官能团兼容性;其次,该方法简单、高效,反应中只需要加入特戊酸碘苯就可以得到产率中等至较好的目标产物。该反应条件比其他合成8-酰胺基喹啉5位磺酰化产物的方法简单,并且能够得到苯胺对位的磺酰化产物,这是其他方法所不能够得到的(Scheme 2)。Scheme 2
[Abstract]:The main content of this paper is the selective carbon-hydrogen bond functionalization mediated by high valence iodine reagents, which are 5-position or p-position amination and sulfonylation of 8-aminoquinoline with aniline, respectively. The amination and sulfonation reaction can take place successfully without metal catalyst or other additives under the mediation of high valence iodine reagent. The specific contents are as follows: 1. N-fluorobis sulfonamide (NFSI) reacts with 8-aminoquinoline or aniline via carbon-hydrogen bond amination with N-fluorobis sulfonamide (NFSI) under the mediation of iodobenzene pivalate with high valence iodide, and 5 or para-position amination products with moderate to better yield are obtained. The reaction conditions are mild, high regioselectivity and good functional group compatibility. The reaction does not require metal catalyst or other oxidant, additive participation, and can be completed in an open system. This method provides an efficient and novel method for the preparation of aromatic amines. On the basis of the previous research results, we continue to explore the application scope of the system of C-H bond functionalization mediated by high valence iodide reagent. The results show that the 5-position or para-position sulfonated products of 8-aminoquinoline and aniline can also be obtained by replacing NFSI with sulfonyl chloride. The method also has high regioselectivity and good functional compatibility for amides and sulfonyl reagents. Secondly, the method is simple and efficient. Iodobenzene pivalate was added to the reaction to obtain the target product with moderate to better yield. The reaction conditions are simpler than other methods for the synthesis of 5-position sulfonated products of 8-aminoquinoline, and aniline para-sulfonated products can be obtained, which is not available by other methods.
【学位授予单位】：湖北工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25
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本文编号：1939156