钌催化炔烃氧化与有机催化醛的酯化反应研究.pdf

钌催化炔烃氧化与有机催化醛的酯化反应研究中文摘要I中文摘要在传统的有机合成方法中,当量试剂参与的反应作为有机合成方法学研究的主要部分,取得了骄人的成果。在改善传统方法的过程中,人们逐渐认识到要努力发展催化过程的反应。本论文主要分为以下两大部分:第一部分主要研究金属钌催化的炔烃氧化为1,2-二酮的氧化反应,同时也对该反应的应用进行了考察。该反应采用极少量的钌化合物作为催化剂,用商业化的氧化剂,在温和的条件下完成了对较大的范围炔烃的转化,并利用该方法,通过“一锅两步”的方法合成了一系列的喹喔啉衍生物。第二部分主要研究了有机分子四丁基碘化铵催化的酯化反应。该反应使用四丁基碘化铵作为催化剂,通过交叉脱氢偶联的方式,将醛和羟基进行直接氧化偶联,以高收率得到相应的酯。同时,通过对反应机理的初步研究,该转化以一种自由基过程进行,实现了自由基的选择性偶联。上述研究主要涉及了有机合成方法学研究的两个主要领域:金属催化与有机催化。在有机合成方法研究未来发展的道路上,将两个领域结合以完成新的转化将成为有机化学发展的新趋势。关键词:金属催化,钌,有机催化,四丁基碘化铵作者:徐元指导老师:万小兵英文摘要钌催化炔烃氧化与有机催化醛的酯化反应研究IIRuthenium-catalyzed Oxidation of Alkynes anocatalytic Esterification of AldehydesAbstractIn traditional organic synthetic methods, stoichiometricreactions have achieved outstanding results as the major research area of anic synthetic methodology. In improving traditional methods, people gradually recognize that it is necessary to develop catalytic poses with two major parts as follows:In the first part we mainly researched ruthenium-catalyzed oxidation of alkynes to 1,2-diketones and studied its application as well. The reaction employed commercial available oxidant with extremely low ruthenium loading to convert a wide range of alkynes in mild condition. Meanwhile, a series of quinoxaline derivatives were synthesized in one pot with two steps using the the second part we focused on the researchof esterification catalyzed anocatalyst tetrabutylammonium iodide. The transformation employed n-tetrabutylammonium iodide as catalyst, and aldehydes coupling with pounds directly via Cross-Dehydrogenative-Coupling process to give corresponding ester in high yield. Moreover,after preliminary exploration the mechanism we tend to believe the transformation went via radical process. Notably, the reaction was realized by selective radical research involved two major fields in organic synthetic methodology: metal catalysis and organoc