节点文献
吡啶C-H键活化及功能化
Pyridine C-H Bond Activation and Functionalizatin
【作者】 公雪;
【导师】 张宏;
【作者基本信息】 东北师范大学 , 分析化学, 2011, 硕士
【摘要】 在本论文中,作者从事了金属钯配合物的合成及催化活性的研究,其中包括吡啶氧化物C-H活化及功能化,以及不对称的C-C偶联反应。第一章,作者详细描述了近年来以过渡金属为催化剂,通过吡啶类化合物的直接C-H活化及功能化合成一系列在医药、生物、农药等领域占有重要地位的含吡啶结构的杂环化合物。第二章,作者以醋酸钯为催化剂,碳酸银为氧化剂,通过吡啶氧化物2-位及吲哚3-位的两次C-H活化,完成了吡啶氧化物与吲哚的氧化偶联反应,合成了一系列3-(2-吡啶氧化物)吲哚类化合物。动力学同位素效应显示,吡啶氧化物的C-H活化包含在反应的决速步中。第三章,作者设计、合成、表征了一类基于含噁唑啉结构的NNN三齿类配体的二价钯配合物。在催化不对称Suzuki-Miyaura偶联反应中,该类钯配合物具有良好的催化活性及立体选择性。
【Abstract】 In this dissertation, my aim is to study synthesis and catalytic application ofpalladium complexes, including pyridine N-oxide C-H functionalization andenantioselectivity C-C coupling reaction.Transition-metal-catalyzed C-H activation and functionalization of pyridinemoiety was reviewed in Chapter 1. By this way, a series of pyridine derivates wereprepared, which play great roles in pharmaceutical and pesticide.Chapter 2 described that Pd(II)-catalyzed oxidative coupling between pyridineN-oxides and N-substituted indoles via two-fold C-H bond activation has beenachieved using Ag2CO3 as an oxidant. Kinetic Isotope Effect (KIE) indicates that thecleavage of the N-oxide C-H bond is involved in the rate-determining step.In Chapter 3, a series of palladium complexes bearing pincer chairal oxazolineligand were designed and synthesized. In asymmetric Suzuki-Miyaura couplingreaction, these palladium complexes have showed high efficiency andenantioselectivity.
【Key words】 Pd-catalyzed; C-H activation; Pyridine oxide; Indole; Oxidative coupling; Oxazolines; Suzuki-Miyaura coupling reaction;