高碘化合物论文：氧化碘苯与四正丁基碘化铵引发的[1,3]氧化环化合成环丙烷和氮杂环丙烷的反应研究.doc

高碘化合物论文：氧化碘苯与四正丁基碘化铵引发的1，3氧化环化合成环丙烷和氮杂环丙烷的反应研究【中文摘要】本论文主要对氧化碘苯与四正丁基碘化铵引发下的氧化环化反应进行了研究。发展了在氧化碘苯与四正丁基碘化铵条件下通过氧化环化合成环丙烷及氮杂环丙烷类化合物的新方法。第一部分工作中,我们研究了在氧化碘苯与四正丁基碘化铵存在下,通过对活泼碳氢键的氧化构建环丙烷结构,串联邻基参与的脱羧反应,立体选择性合成了多取代环丙烷羧酸酯,并培养了主要产物的单晶。我们对该反应的机理进行了研究,对反应过程中产生的三种化合物之间的转化做了探索,从而提出了先通过氧化环化,然后在酰胺氢的参与下脱羧得到环丙烷羧酸酯的反应机理。该反应得到了顺式的环丙烷衍生物,反应条件温和,产率高,选择性好。接下来,我们研究了在氧化碘苯与四正丁基碘化铵引发下实现的分子内氧化环化制备苯甲酰基保护的氮杂环丙烷类化合物,反应底物适用性好,同时发现反应具有一定的底物可控性,当原料结构中使用乙酰丙酮代替丙二酸二乙酯时,能够选择性得到五元环产物为主,有关反应我们将做进一步的研究。【英文摘要】This thesis focused on the cyclization reaction induced by the combination of PhIO and TBAI. We developed synthesis methods based on the 1,3 oxidative cyclization which induced under the PhlO/TBAI condition, and synthesized compounds of cyclopropanes and aziridines.In the first part, we developed a facile synthesis of cyclopropanecarboxylates through a tandem PhlO/TBAI induced oxidative cyclization and a subsequent neighboring group-assisted decarboxylation of the Michael adducts of 2-cyanoacetamides with,-unsaturated malonates. Furthermore, it affords the desired highly functionalized cyclopropanes in moderate to good yields and with excellent diastereoselectivities. The products were proved to be cis-configuration with the X-ray Diffraction analysis. According to the transformation among three compounds which we got from the same material, we raised a plausible reaction mechanism that the reaction underwent an intramolecular oxidative cyclization and a subsequent amide-assisted decarboxylation. In addition, the reaction proceeds smoothly under mild conditions and with good functional group tolerance.In the second part, we studied an efficient 1,3 oxidative cyclization of amidoalkylation adducts of activated methylene compounds with the combination of PhIO and a catalytic amount of TBAI under neutral conditions. And we found that the main products would be oxazolines when we changed part of the constitution of the beginning compounds from diethyl malonate to acetylacetone. The reaction also affords products in moderate to excellent yields. The scope and synthetic application are continued to be studied.【关键词】高碘化合物 氧化反应 环化反应 环丙烷 氮杂环丙烷【英文关键词】hypervalent Iodine oxidative reaction cyclization reaction cyclopropane aziridine【目录】氧化碘苯与四正丁基碘化铵引发的1，3氧化环化合成环丙烷和氮杂环丙烷的反应研究摘要4-5Abstract5第一章:前言6-15参考文献13-15第二章:氧化碘苯与四正丁基碘化铵引发的氧化环化脱羧串联反应研究15-29第一节:环丙烷骨架构建方法介绍15-19第二节:氧化碘苯与四正丁基碘化铵引发的氧化环化脱羧串联反应合成多取代环丙烷类化合物的反应研究19-27参考文献27-29第三章:氧化碘苯与四正丁