在催化体系可回收和无配体条件下溴化四丁基铵中钯催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应

我们发展一种在催化体系可回收和无配体条件下溴化四丁基铵（TBAB）中钯催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应方法。我们发现水的量对反应有很大的影响。当水的用量为1 %（质量比）时,反应的结果最好。在3 mol%的醋酸钯和1.5 g的TBAB（含1%的水）,一系列卤代芳烃与芳基硼酸的顺利地发生Suzuki-Miyaura交叉偶联反应,得到中等及良好的产率。而且在溴代芳烃和活泼的氯代芳烃的交叉反应中,Pd(OAc)2/TBAB催化体系可以回收重复使用多次,并且催化活性基本不变。     

胺作为配体在钯催化偶联反应中应用

对近期我们研究小组及其它研究小组在利用胺作为钯催化偶联反应的配体研究进展进行了总结. 钯/胺作为催化体系主要应用的偶联反应包括: Suzuki-Miyaura交叉反应, Sonogashira交叉反应, Stille交叉反应, Hiyama交叉反应和Heck反应. 研究结果表明胺可以作为价廉和高效的配体促进钯催化交叉偶联反应.     

醚功能化的膦配体的合成、负载及其在钯催化的Suzuki-Miyaura反应中的应用

合成了一种新的醚功能化的二茂铁膦3,连到Merrifield树脂上形成负载型的膦配体4;分别开展了膦配体3及其负载型的4在钯催化的Suzuki-Miyaura偶联反应中催化研究;发现相应形成的均相和多相钯催化剂可高产率地催化一系列的溴代芳烃与芳基硼酸偶联形成相应的联芳烃,以及负载型催化剂在不补加钯时具有一定的循环性能.     

四乙烯五胺功能化纤维素负载纳米钯催化剂的制备及其对Suzuki反应催化性能的研究

利用四乙烯五胺对环氧化纤维素进行功能化改性,并以其为载体在95％乙醇溶液中现场还原氯化钯制备出四乙烯五胺功能化纤维素负载的纳米钯催化剂.利用IR,XRD,SEM,TEM等分析方法对其进行了表征并用于催化Suzuki交叉偶联反应.实验表明,该催化剂在温和条件下能有效催化卤代芳烃与芳基硼酸的Suzuki交叉偶联反应,该催化剂经回收重复利用5次后,仍具有较高的催化活性.     

浅谈国外“Suzuki-Miyaura金属偶联反应”的教学设计思路

Suzuki-Miyaura金属偶联反应是在零价钯配合物的催化下,芳基硼酸或硼酸酯与卤代芳烃发生交叉偶联的过程。该反应具有很强的底物适应性和官能团容忍性,广泛应用于众多天然产物与有机材料的合成。鉴于反应的重要性,近年来国外高校逐渐尝试将Suzuki-Miyaura反应引入到本科生的有机实验教学中。本文针对2000年后Journal of Chemical Education期刊中涉及的Suzuki-Miyaura反应,分别从反应条件、后处理和表征方法、实验拓展等多个方面进行了比较和归纳,并对其设计理念和教学特色进行了综述。     

发展高效的不对称Suzuki-Miyaura偶联反应及其合成应用

为解决不对称Suzuki-Miyaura交叉偶联反应中活性和选择性问题,我们设计并发展了一系列结构刚性的手性联芳基单膦配体.在发展高活性的大位阻交叉偶联反应方面,成功地实现了邻位四取代芳基芳基之间的Suzuki-Miyaura交叉偶联,并发展了官能团化的大位阻交叉偶联,在邻位二取代芳基溴苯与二级烷基硼酸之间的大位阻芳基烷基交叉偶联中也取得进展.在发展高立体选择性的交叉偶联反应方面,我们采用手性大位阻单膦配体和底物间次级作用相结合的设计理念,利用苯并噁唑啉酮辅基和芳基间的π-π作用,成功地发展了高立体选择性的邻位酰基化芳基芳基间不对称Suzuki-Miyaura偶联;利用极性基团双(2-氧代-3-噁唑烷基)次磷酰基(BOP)辅基和芳基间的极性π作用,成功地实现了应用性强的邻位氧基取代芳基芳基间高效不对称Suzuki-Miyaura偶联.最后我们首次将高效的不对称SuzukiMiyaura偶联方法学应用于天然产物合成,完成了手性联芳基天然产物Korupensamine A和Korupensamine B的高效不对称合成,并完成天然产物Michellamine B的立体选择性全合成.     

乙二胺功能化纤维素负载纳米钯催化Suzuki反应的研究

以氯化纤维素为原料, 通过与乙二胺的胺化反应制得乙二胺功能化纤维素(Cell-EDA), 然后再将胺化纤维素在氯化钯乙醇溶液中反应可以方便制备得到乙二胺功能化纤维素负载的纳米钯催化剂(Cell-EDA-Pd0). 用SEM, TEM等分析方法对所制备的催化剂进行了表征; TEM分析表明乙二胺功能化纤维素负载的纳米钯呈球形, 粒径在10～20 nm左右. 实验结果表明, Cell-EDA-Pd0催化剂对空气稳定, 无需在惰性气体的保护下就能有效地催化芳基硼酸与卤代芳烃的Suzuki交叉偶联反应, 催化剂易回和收重复使用, 催化剂重复使用6次催化活性没有明显降低.     

铃木-宫浦羰化反应在合成二芳基甲酮中的应用

近年来,钯催化的芳基卤化物和芳基硼酸化合物的羰化偶联反应发展十分迅速。到目前为止,大量硼酸化合物、钯催化剂前体、配体和羰基源被用来合成二芳基甲酮,此类化合物在工业中间体、染料、药剂、天然产物等领域有着广泛的应用。本文从钯催化剂体系、转金属促进剂、羰基源及其应用方面综述了铃木-宫蒲（Suzuki-Miyaura or Suzuki）羰化反应的研究进展。钯催化剂体系从均相和非均相体系两方面介绍,其中均相催化体系包括钯催化剂前驱体、磷配体、氮杂卡宾配体的研究进展;非均相催化体系主要介绍了活性炭、石墨烯、官能化硅胶、四氧化三铁等载体多种固载钯催化剂的应用。特戊酸添加剂可改善转金属化过程,有效加速羰化偶联反应。经典的羰化Suzuki反应一般需要气体钢瓶提供压力较高的一氧化碳气体。尽管近期一些研究实现了常压一氧化碳气球作为羰基供给源,使用一氧化碳释放分子（CO-releasing molecule,CORM）替代剧毒危险的一氧化碳气体可实现更为安全绿色的羰化反应进程。在双管反应器中,有机CORM可控降解释放一氧化碳,为钯催化羰基偶联反应提供CO。在微波辐射下,过渡金属羰基化合物可为羰基化反应原位直接提供CO。     

氧官能化的膦配体在钯催化的Suzuki-Miyaura反应中的应用

合成了带甲氧基和羟基官能团的二茂铁膦配体, 评价了它们在钯催化的Suzuki-Miyaura偶联反应中的性能, 发现带甲氧基的膦配体对钯催化的Suzuki-Miyaura偶联反应有更好的性能, 可催化富电子溴代芳烃和缺电子氯代芳烃与苯硼酸反应高产率地生成相应的联芳烃产物.     

氯化钯催化的交叉偶联反应

钯催化的交叉偶联反应已经成为有机合成化学中构建C-C键最重要的方法之一.其中,氯化钯及其配合物所组成的催化体系具有高效、高选择性、稳定以及价廉等优点,因而在交叉偶联反应中得到较为广泛的应用.综述了氯化钯及其配合物催化的交叉偶联反应,其中包括Suzuki反应、Stille反应、Hiyama反应和Kumada反应等.     

An Efficient Palladium and Bis(2‐pyridylmethyl)amine‐based System for Suzuki‐Miyaura Cross‐Coupling under Aqueous and Aerobic Condition

A novel PdCl₂/bis(2‐pyridylmethyl)amine‐based ligand ( 1 ) catalytic system, which is water‐soluble and air‐stable, has been successfully synthesized and applied for Suzuki‐Miyaura cross‐coupling reaction. In the presence of catalytic amount of PdCl₂/ 1 system, arylboronic acids can couple with a wide range of aryl halides, including aryl bromides and aryl chlorides. The reactions proceed under mild conditions to give excellent yields, and a wide range of functionalities is tolerated.     

Alcoholic solvent‐assisted ligand‐free room temperature Suzuki–Miyaura cross‐coupling reaction

We have observed the enhancing effect of alcoholic solvents in palladium‐catalysed ligand‐free Suzuki–Miyaura reactions. No extra additives or ligands are required for the Suzuki–Miyaura reaction of aryl bromides with arylboronic acids when we carried out the reaction in alcoholic or aqueous alcoholic solvents. Moreover, ethanol or aqueous ethanol is found to be a very good solvent for the Suzuki–Miyaura reaction involving electronically diverse aryl bromides and arylboronic acids under mild and ligand‐free conditions with low catalyst loading. It is observed from Hg(0) poisoning tests that the in situ generated palladium(0) species is the actual catalytic species for the reaction. Copyright © 2015 John Wiley & Sons, Ltd.     

Solvent‐Free,Palladium‐Catalyzed Suzuki–Miyaura Cross‐Couplings of Aryl Chlorides with Arylboronic Acids

Pd(MeCN)₂Cl₂/PCy₃ was found to be an efficient catalytic system for the Suzuki–Miyaura cross‐couplings of aryl chlorides with arylboronic acids under solvent‐free conditions. Furthermore, the presence of the conventional solvents had deleterious effect on the reaction. In the presence of Pd(MeCN)₂Cl₂, PCy₃, and TBAF (tetra‐n‐butylammonium fluoride), a number of aryl chlorides including heteroaryl chlorides were coupled with arylboronic acids or heteroarylboronic acids smoothly to afford the corresponding products in moderate to excellent yields.     

Synthesis of Terphenyl Derivatives by Pd‐Catalyzed Suzuki‐Miyaura Reaction of Dibromobenzene Using 2N2O‐Salen as a Ligand in Aqueous Solution

A simple and efficient catalytic system for Na₂PdCl₄ catalyzing the Suzuki‐Miyaura reaction of dibromobenzene and arylboronic acid has been developed by using 2N2O‐salen as a ligand in H₂O/EtOH (V:V=4:1) at 100°C. Using this method, the reactions of substrates containing sterically demanding ortho substituents (e.g. dibromobenzene and/or arylboronic acids) proceeded efficiently, with the corresponding terphenyl derivatives being produced in moderate to excellent yields. Furthermore, this method offers interesting features for the multi‐gram scale synthesis of terphenyl compound.     

Synthesis of 4‐substituted styrene compounds via palladium catalyzed Suzuki–Miyaura reaction using bidentate Schiff base ligands

Air‐stable symmetric Schiff base have been synthesized and proved to be efficient ligands for Suzuki–Miyaura reaction between aryl bromides and arylboronic acids using PdCl₂(CH₃CN)₂ as palladium source under aerobic conditions. The coupling reaction proceeded smoothly using N,N‐bis(anthracen‐9‐ylmethylene)benzene‐1,2‐diamine (L₇) as ligand to provide 4‐substituted styrene compounds in good yields. Copyright © 2009 John Wiley & Sons, Ltd.     

Facile synthesis of alkynyl‐, aryl‐ and ferrocenyl‐substituted pyrazoles via Sonogashira and Suzuki–Miyaura approaches

A concise and efficient synthesis of densely substituted novel pyrazoles with alkynyl, aryl and ferrocenyl functionalities is reported, providing a platform for biological studies. The general strategy involves Sonogashira and Suzuki–Miyaura cross‐coupling reactions of easily obtainable 5‐ferrocenyl/phenyl‐4‐iodo‐1‐phenylpyrazoles with terminal alkynes and boronic acids, respectively. The starting 4‐iodopyrazoles were synthesized by electrophilic cyclization of α,β‐alkynic hydrazones with molecular iodine. Sonogashira reactions have been achieved by employing 5 mol% PdCl₂(PPh₃)₂, 5 mol% CuI, excess Et₃N and 1.2 equiv. of terminal alkyne, relative to 4‐iodopyrazole, in tetrahydrofuran at 65 °C, while Suzuki–Miyaura reactions have been accomplished using 5 mol% PdCl₂(PPh₃)₂ and 1.4 equiv. of both boronic acid/ester and KHCO₃, with respect to 4‐iodopyrazole, in 4:1 dimethylformamide–H₂O solution at 110 °C. Both Sonogashira and Suzuki–Miyaura coupling reactions have proven effective for the synthesis of alkynyl‐, aryl‐ and ferrocenyl‐substituted pyrazoles and demonstrated good tolerance to a diverse range of substituents, including electron‐donating and electron‐withdrawing groups. These coupling approaches could allow for the rapid construction of a library of functionalized pyrazoles of pharmacological interest. Copyright © 2016 John Wiley & Sons, Ltd.     

Suzuki–Miyaura reactions promoted by a PdCl2/sulfonate‐tagged phenanthroline precatalyst in water

This work reports Suzuki–Miyaura cross‐coupling reactions of arylboronic acid with aryl halide or aryl dibromide mediated by PdCl₂ (0.05 mol%) and sodium 4‐(1H‐imidazo[4,5‐f][1,10]phenanthrolin‐1‐yl)butane‐1‐sulfonate (0.05 mol%) at 100 °C in water. The corresponding cross‐coupling products were obtained in good to excellent yields. The catalytic system was recovered from the organic products by extraction with ether and the residual aqueous catalyst phase showed high activity after reuse of at least four cycles. Copyright © 2014 John Wiley & Sons, Ltd.     

A highly active palladium(II)–bis(oxazoline) catalyst for Suzuki–Miyaura,Mizoroki–Heck and sonogashira coupling reactions in aqueous dimethylformamide

An efficient catalytic system based on a new palladium–bis(oxazoline) ( Pd-BOX-1 ) complex has been developed. The complex Pd-BOX-1 adopts a legless chair‐type structure where the distorted square planar [PdN₂Cl₂] moiety and the benzene ring spacer represent the seat and the chair back, respectively. The catalytic activity of Pd-BOX-1 has been investigated in dimethylformamide–water under aerobic and mild conditions in Suzuki–Miyaura coupling reactions of arylboronic acids with aryl iodides, aryl bromides and aryl chlorides, Mizoroki–Heck coupling reactions of aryl halides with styrene derivatives, and Sonogashira coupling reactions of aryl halides with terminal alkynes. A wide range of functional groups as substituents on the arylboronic acids and aryl halides were considered. Pd-BOX-1 demonstrates exceptional air and moisture stability. Of note, the catalyst system based on Pd-BOX-1 shows high recycling ability in Suzuki–Miyaura coupling reactions in dimethylformamide–water without any loss in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Highly Efficient Palladacycle/Dihydroimidazolium Chloride System for the Suzuki‐Miyaura Cross‐Coupling of Aryl Halides (I,Br, Cl) with Arylboronic Acids

A combination of a tertiary amine‐based palladacycle and an N‐heterocyclic carbene ligand precursor ( 1 , N,N‐bis‐mesityl‐4,5‐dihydroimidazolium chloride) has been applied to catalyze the Suzuki‐Miyaura cross‐coupling of aryl halides with arylboronic acids. The substrate scope is general: a variety of electron rich and deficient aryl halides (I, Br, Cl) and arylboronic acids were found to undergo the cross‐coupling reaction in good to excellent yields at low catalyst loading of 0.01–1 mol%.