【作者】 戴学新；

【导师】 李毅群；

【作者基本信息】 暨南大学 ， 有机化学， 2011， 硕士

【摘要】 Suzuki反应和Heck反应是现代有机合成中重要的反应,在天然产物、医药和高分子的合成中有着极其重要的地位。近年来,水相中的C-C偶联反应受到了越来越多研究者的关注。我们将同时具有配位功能和相转移作用的功能化季铵盐卤化1-烷基-4-氮杂-1-氮鎓双环[2.2.2]辛烷(以下简称为DABCO季铵盐)应用于水相中的Suzuki和Heck偶联反应。主要内容包括以下四章：第一章概述了水相中Suzuki反应和Heck反应的研究进展及课题提出的意义。第二章采用水为反应介质,在溴化1-丁基-4-氮杂-1-氮鎓双环[2.2.2]辛烷([BDABCO]Br)存在下,纳米钯能有效地催化一系列卤代芳烃与芳基硼酸发生Suzuki交叉偶联反应,以良好产率生成联苯类产物。该催化体系nano-Pd0/[BDABCO]Br/H2O对底物官能团无影响,产物可通过简单萃取分离,产率优良,对环境友好。第三章在溴化1-十二烷基-4-氮杂-1-氮鎓双环[2.2.2]辛烷([DDABCO]Br)存在下,采用水为反应介质,纳米钯能够有效地催化Heck反应、Suzuki反应和苯硼酸的自偶联反应。nano-Pd0/[DDABCO]Br/H2O催化体系具有产率较高,稳定性好,重复使用6次,活性没有明显降低。第四章研究了DABCO功能化二氧化硅负载纳米钯催化剂催化Suzuki反应。结果表明该催化剂能很好地催化一系列卤代芳烃与苯硼酸的Suzuki反应,以36-99%的产率生成相应的联苯化合物。该催化剂具有制备简单,催化活性好,催化反应条件温和、操作简单、产率高、可以回收利用和环境友好等特点。更多还原

【Abstract】 The palladium catalyzed Suzuki and Heck reactions are well-established methodlogies in mordern organic synthesis. The coupling products are found to have good applications as intermediates in the preparation of natural products, medicines and polymers. We have studied the application of 1-akyl-4-aza-1-azoniabicyclo[2.2.2]octane halide in Suzuki and Heck reaction. This thesis is divided into four chapters.In chapter 1, we have outlined the recently development and the significance of the Suzuki and the Heck reactions in aqueous media.In chapter 2, a practical procedure for nano-palladium catalyzed Suzuki cross-coupling reaction in the presence of 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide ([BDABCO]Br) in water media was investigated. The combined nano-Pd0/[BDABCO]Br/H2O catalytic system exhibited excellent functional group tolerance for various aryl halides and arylboronic acids and afforded moderate to excellent yields of the corresponding biphenyl products under air conditions. This protocol provided several advantages such as excellent yield, short reaction time, simple experimental and work-up procedure, and benign to environment.In chapter 3, a practical procedure for nano-palladium catalyzed Heck, Suzuki cross-coupling reaction and homocoupling of phenylboronic acid in the presence of 1-dodecyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide ([DDABCO]Br) in water media was investigated. The combined nano-Pd0/[DDABCO]Br/H2O catalytic system afforded good yields of the corresponding products under air conditions. Furthermore, the catalyst system can be reused for at laest 6 recycles without losing its activities.In chapter 4, we have prepared and characterized palladium complex on the surface of silica-supported 1,4-diazabicyclo[2.2.2]octane(Pd@SiO2-DABCO), and investigated its performance in Suzuki cross-coupling reactions. The as-prepared catalyst (Pd@SiO2-DABCO) afforded 36-99% yields of the corresponding biphenyl products under air conditions. This catalyst has the advantages such as simple operation, high activity, recycling and reuse of catalysts and environmentally friend.更多还原