卤代芳烃和苯硼酸的Suzuki偶联反应研究进展

Suzuki偶联反应是形成C-C键的有效方法之一,在天然产物合成和药物中间体合成中发挥着重要作用,近年来一直是有机化学和催化化学的研究热点.本文综述了最近几年来Suzuki偶联反应及其在有机合成中的应用研究进展,叙述了Suzuki偶联的原理,对以Pd、Ni、Cu及其它催化剂在Suzuki偶联反应中的应用进行了重点论述,...     

Suzuki偶联反应中钯配合物催化剂的研究进展

Suzuki偶联反应是在零价钯配合物催化剂的催化下,芳基硼酸与卤代芳烃进行的交叉偶联反应,可以高效、高选择性地构建C-C键.钯配合物催化剂对Suzuki偶联反应的活性和选择性起着决定性的影响,是研究Suzuki偶联反应的关键.对含有膦配体、N-卡宾配体、亚胺配体、胺配体和其它配体的钯配合物催化剂催化效果进行了综述.     

浅议钯催化的偶联反应

介绍了以三位有机化学家的名字命名的钯催化偶联反应，即Heck偶联、Suzuki偶联、Negishi偶联反应，并对反应的适用范围、反应机理等进行了介绍。     

无机物载体负载钯催化Suzuki偶联反应研究进展

Suzuki芳基偶联反应是构建联苯芳烃和多联苯芳烃结构单元的重要反应之一。传统的Suzuki偶联反应的催化剂多数是均相催化剂,催化活性很高,但存在催化剂回收困难、污染产品等缺点。固定化技术可有效地解决上述问题,已成为Suzuki偶联反应的催化剂研发的热点。综述了近些年来以无机碳、金属氧化物、多孔分子筛等无机材料为载体负载钯催化Suzuki偶联反应的最新进展。     

离子液体在Suzuki偶联反应中的应用

过渡金属Pd催化的Suzuki偶联反应是构建C-C键的重要反应之一,在许多领域都有着广泛应用.在离子液体中进行的Suzuki偶联反应具有反应活性高、选择性好等特点.含有Pd配体的功能化离子液体直接催化Suzuki偶联反应可提高催化活性,容易实现产物与催化剂分离.固载化离子液体可有效地解决催化剂难以重复使用的问题.     

常见含氮配体在钯催化Suzuki反应中的研究进展

常见的含氮配体如席夫碱类化合物用于钯催化Suzuki反应,由于其性能稳定,催化反应过程不产生有毒物质等优点,近年来受到化学工作者的广泛关注。本论文简要总结了近年来用于钯催化Suzuki反应的常见含氮配体催化性能,讨论了常见含氮配体用于钯催化Suzuki偶联反应中催化的活性以及反应产物的研究价值,文献发现,大部分的催化剂对Suzuki偶联反应具有极高的催化效果。     

钯催化Suzuki偶联反应的研究进展

金属Pd催化的Suzuki偶联反应是碳-碳偶联反应中重要的反应之一。综述了近年来Pd催化Suzuki偶联反应的研究进展,其中包括Suzuki反应机理、配体种类及其在有机合成中的应用。介绍了含N、P配体的钯催化剂和碳纳米管、磁性材料、多孔材料、水滑石、金属氧化物、高分子材料等负载的无配体钯催化剂的研究进展。     

咪唑并[1, 2-a]吡啶甲酸衍生物的合成与表征

以3-三氟甲基-2-氨基吡啶为原料,通过NBS选择性溴化,再与溴代丙酮酸甲酯通过“一锅法”进行烷基化-环化反应,之后经选择性氯化、Suzuki偶联反应和水解,合成了咪唑并[1,2-a]吡啶甲酸衍生物。反应总收率达到36.5%。并对Suzuki偶联反应的催化剂和反应条件进行了探讨。     

钯催化芳基硼酸与芳卤偶联反应的工业应用新进展

钯催化芳基硼酸与芳卤偶联反应(即Suzuki反应)是用于碳碳键形成的重要方法之一,在有机合成中应用十分广泛。本文着重综述了钯催化Suzuki偶联反应在工业化应用方面的一些新进展。     

离子液体中偶联反应的研究进展

综述了近年来离子液体作为反应介质在Suzuki偶联、Heck偶联、Sonogashira偶联、碳-杂原子交叉偶联和Negishi偶联等反应中的研究进展。     

Highly active palladium nanoparticles immobilized on knitting microporous organic polymers as efficient catalysts for Suzuki–Miyaura cross-coupling reaction

By encaging the Pd nanoparticles in the interior space of the hypercrosslinked microporous organic polymer, we successfully prepared a novel eco-friendly heterogeneous catalyst for Suzuki cross-coupling reaction. The catalyst afforded fast conversions for the Suzuki cross-coupling reaction even at a loading of 0.05 mmol% Pd, and the turnover frequency for the reaction could be up to 61,353 h^?1. Furthermore, this catalyst is stable enough to be reused more than five times with no appreciable activity decrease. This work provides a method for fabricating highly active microporous organic polymer encapsulated Pd catalysts for Suzuki cross-coupling reaction and resolve the problem of industrialization in traditional active carbon catalysts.     

The effect of ionic liquids on product yield and catalyst stability

The effect of ionic liquids on product yield and catalyst stability has been investigated through Suzuki cross-coupling of phenylboronic acid and 4-bromoacetophenone in organic solvents, ionic liquids and mixtures of organic solvents and ionic liquids.     

负载钯及非钯型Suzuki偶联反应催化剂体系的研究进展

Suzuki偶联反应是现代有机合成化学中构筑碳碳键的最有效方法之一。传统的Suzuki反应催化剂主要是Pd(PPh3)4、Pd(OAc)2等均相催化剂。这类催化剂的活性较高,但其价格高、化学稳定性较差、难以与反应液分离和回收再利用等缺点也是不容忽视的。近年来,人们开发了一系列具有不同的钯材料载体(碳材料、高分子材料以及无机材料等)的非均相催化剂体系,以及基于Ni、Cu、Mn等过渡金属的新型催化体系。这些新型的催化剂体系的发展有效地解决了上述均相催化剂的不足。综述了近来Suzuki反应在负载催化剂和非钯催化剂方面的研究进展。     

Dppc~+PF_6~--Pd(dba)_2催化的水相中的Suzuki偶联反应

文章报道了二茂钴阳离子双膦配体dppc+PF6-与Pd(dba)2组成的催化剂在纯水中催化Suzuki反应的活性,以三乙胺为碱,该催化剂体系对于不同的溴代底物与苯基硼酸在120℃反应3h,能以中等到较高的产率得到相应的偶联产物。该催化体系既避免了使用毒性、易挥发和易燃的有机溶剂,并且形成的离子型催化剂由于极性比较大,不溶于乙醚或正己烷等弱极性溶剂,很容易实现催化剂与底物的分离。     

Pd@SnO2催化剂的制备及其应用

首先合成了一种具有多孑L结构的SnO2,进而以此为金属钯的载体,制备了一种非均相钯催化剂Pd@SnO2,并将其应用于Suzuki偶联反应中.研究结果表明,所合成的Pd@SnO2非均相催化剂在Suzuki反应后易回收,且可被多次使用,同时该催化剂在Suzuki反应中具有很好的底物普适性.     

Sequential Processes in Palladium-Catalyzed Silicon-Based Cross-Coupling

Although developed somewhat later, silicon-based cross-coupling has become a viable alternative to the more conventional Suzuki–Miyaura, Stille–Kosugi–Migita, and Negishi cross-coupling reactions because of its broad substrate scope, high stability of silicon-containing reagents, and low toxicity of waste streams. An empowering and yet underappreciated feature unique to silicon-based cross-coupling is the wide range of sequential processes available. In these processes, simple precursors are first converted to complex silicon-containing cross-coupling substrates, and the subsequent silicon-based cross-coupling reaction affords an even more highly functionalized product in a stereoselective fashion. In so doing, structurally simple and inexpensive starting materials are quickly transformed into value-added and densely substituted products. Therefore, sequential processes are often useful in constructing the carbon backbones of natural products. In this review, studies of sequential processes involving silicon-based cross-coupling are discussed. Additionally, the total syntheses that utilize these sequential processes are also presented.     

负载钯催化Suzuki偶联反应的研究进展

过渡金属钯催化C-C偶联反应在有机合成中具有重要地位,负载型钯催化剂具有分离简便、可重复使用等优点,引起了人们的关注。综述了不同载体催化剂催化Suzuki偶联反应的研究进展。     

Transition-metal-free oxidative coupling reactions for the formation of C-C and C-N bonds mediated by TEMPO and its derivatives

The application of nitroxides for the development of new synthetic methods and their implementation in polymer chemistry, material science and beyond is one of the major research topics in our laboratory in the institute of organic chemistry at the WWU Münster. This short review focuses on our recent progress towards nitroxide-based transition-metal-free oxidative coupling reactions. The demand for organic surrogates for transition metals in such transformations is in our eyes unquestionable, since environmental and economic issues have become progressively more important in recent years. For this purpose, the 2,2,6,6-tetramethylpiperidine-N-oxyl radical (TEMPO) is shown to be a highly efficient oxidant for the homo- and cross-coupling of Grignard reagents. This powerful C-C bond forming strategy allows the generation of conjugated polymers from bifunctional Grignard reagents. Moreover, cross-coupling of alkynyl Grignard compounds and nitrones can be accomplished under aerobic atmosphere with catalytic amounts of TEMPO. It is also shown that TEMPO-derived N-oxoammonium salts can act as suitable oxidants for formation of C-N bonds between non-preactivated benzoxazoles and secondary amines under metal-free conditions.     

Palladium-catalyzed efficient Suzuki–Miyaura reaction of potassium aryltrifluoroborates in water

An efficient and environment-friendly protocol has been developed for the palladium-catalyzed Suzuki–Miyaura reaction of potassium aryltrifluoroborates with (hetero)aryl halides in water without any additive. This method allows the preparation of a variety of biaryls and heterobiaryls in excellent yields. In addition, the cross-coupling product can be isolated in good yields and high purity by simple filtration and recrystallization as the reaction was performed on gram scale.