Glaser反应研究新进展

Glaser偶联反应是合成二炔化合物的重要反应,广泛应用于有机合成、材料化学等领域.介绍了近年来Glaser偶联反应中溶剂、氧化剂、底物等领域的研究新进展,指出Glaser偶联反应在不断加深其各方面绿色化研究的同时,多功能团底物的Glaser偶联反应与不对称的Glaser偶联反应也值得关注.     

Ni催化的Suzuki偶联反应

本文主要对Ni催化的Suzuki偶联反应的发展历程和近年来碳卤键断裂类、碳氧键断裂类、碳碳键断裂类、碳氮键断裂类和碳硫键断裂类Ni催化Suzuki偶联反应进行总结。通过近十年研究,各类新型催化剂、配体、添加剂不断被开发,使反应活性大为提高,反应条件越来越温和。对目前认为Ni催化的Suzuki偶联反应的机理进行了梳理,发现Ni催化的Suzuki偶联反应催化剂循环方式有两种,即Ni(0)/Ni(Ⅱ)循环和Ni(Ⅰ)/Ni(Ⅲ)循环。因此,本文认为研究和发展价廉的金属Ni催化剂是研究Suzuki偶联反应的一个重要方向,未来Ni催化Suzuki偶联反应的研究将会集中在机理探究、新型催化剂和配体设计、多类型碳碳键构建(Csp~2-Csp~3、Csp~3-Csp~3)以及广泛底物的不对称Ni催化的Suzuki偶联反应。     

Suzuki偶联反应的最新研究进展

Suzuki偶联反应是合成联芳烃化合物的最有效方法之一,近几年来一直是催化化学和有机化学的研究热点.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.     

铜催化Ullmann C-N偶联反应的研究进展

铜催化Ullmann C-N偶联反应是一个重要的形成C—N键的有机合成反应。研究表明,合适的配体可以在很大程度上促进铜或铜盐催化的反应活性。新型的配体不断涌现,主要包括N-N、N-O和O-O双齿型配体,极大地推动了铜催化化学的发展。本文综述了添加不同结构配体的铜催化C-N Ullmann偶联反应,并对Ullmann偶联反应的发展前景作了展望。     

介孔TiO2担载Cu（OH）2及其催化炔烃氧化偶联反应

在有序介孔TiO₂中原位担载了高分散的Cu（OH）₂,并将其应用于炔烃的氧化偶联（Glaser）多相催化反应,该催化剂表现出很高的催化活性.Cu（OH）₂为催化剂的主要活性组分,TiO₂的有序介孔和较大的比表面积有利于Cu（OH）₂的分散以及反应物和产物的扩散,具有重要的应用前景.     

光催化有机物偶联/芳构化放氢反应研究进展

光催化氧化还原反应具有绿色、高效、安全等优势,已经在有机化学中得到广泛关注.介绍了基于光催化的偶联/芳构化放氢反应,通过使用光催化剂/催化剂的双催化体系,可用于光催化有机碳-碳和碳-杂原子成键反应,且反应中氢气是唯一的副产物.强调了有机光氧化还原体系的构建与催化机理.     

固相有机合成中钯催化的交叉偶联反应研究进展

过渡金属钯催化交叉偶联反应是形成碳一碳键的一种十分有效的方法,因此钯催化的C—C偶联反应引起了更多人们的广泛关注,并发展了多种不同的C—C偶联反应,包括Heck反应、Negishi反应、Suzuki偶联和Stille偶联等。固相有机合成具有反应条件温和、可使多种活性官能团兼容、受空间位阻影响小、具有高度的化学选择性、毒...     

铃木偶联反应构筑卟啉阵列的研究进展

卟啉阵列是通过桥接单元或键组装而成的多卟啉体系,其电子性质取决于桥接单元以及卟啉连接的位置。由于电子相互作用的卟啉阵列在光电子器件、传感器、光伏电池、非线性光学材料以及光动力治疗的染料等方面的潜在应用价值,在过去的几十年中,科学家们对其进行了大量探索。卟啉阵列的构筑主要包括非共价组装与共价组装两种方式,前者相对容易但构筑的阵列稳定性较差,后者相对较难但构筑的阵列稳定性较好。铃木偶联是指用零价钯催化卤代烃与烃基硼酸或硼酸酯交叉偶联的反应,它是构筑结构多样、性质各异的卟啉阵列的有效手段。本文主要对其近年来在构筑多卟啉阵列方面的研究进展进行综述。最后,展望了铃木偶联构筑卟啉阵列的发展趋势。     

铁催化的交叉偶联反应研究进展

过渡金属催化的交叉偶联反应具有反应条件温和、操作简单、底物范围广等特点而备受关注,其中,铁在地球上存储丰富、廉价、无毒、对环境友好,商品化的铁盐和含铁化合物种类繁多,是一种可供选择的、绿色的、较为理想的催化剂。 近年来铁作为催化剂应用于交叉偶联反应的相关报道逐渐增多,本文根据铁催化剂的不同种类,综述了近年来铁盐催化交叉偶联反应的研究进展,期望为相关的研究工作提供参考。     

负载钯催化的Suzuki偶联反应研究进展

负载钯催化的Suzuki偶联反应,由于产物易分离、催化剂可重复使用,已引起人们的广泛关注.综述了近年来负载钯催化的Suzuki偶联反应研究进展,载体包括活性碳、金属氧化物、硅铝酸盐微孔分子筛、二氧化硅材料、活性粘土和聚合物等.     

Nickel Chloride Promoted Glaser Coupling Reaction in Hot Water

A Glaser coupling reaction of terminal alkynes in the presence of nickel chloride withoutany organics and bases in hot water has been developed, which produces the correspondinghomo-coupling products in good yields.     

Glaser Coupling Reaction without Organic Solvents and Bases under Near-critical Water Conditions

A Glaser coupling reaction of terminal alkynes in the presence of cupric chloride without organic solvents and bases under near-critical water has been developed.     

Silver‐catalyzed Glaser coupling of alkynes

Excellent yields were obtained from the silver nitrate‐catalyzed homocoupling reaction of alkynes in N,N‐dimethylformamide using triphenylphosphine as ligand. This safe and simple silver catalytic system has been employed in a safe and efficient protocol for the synthesis of various 1,3‐diyne products from the corresponding aromatic or aliphatic alkynes with good air stability and absence of side products. Copyright © 2015 John Wiley & Sons, Ltd.     

Adapting the Glaser Reaction for Bioconjugation: Robust Access to Structurally Simple,Rigid Linkers

Copper‐mediated coupling between alkynes to generate a structurally rigid, linear 1,3‐diyne linkage has been known for over a century. However, the mechanistic requirement to simultaneously maintain Cu^I and an oxidant has limited its practical utility, especially for complex functional molecules in aqueous solution. We find that addition of a specific bpy‐diol ligand protects unprotected peptides from Cu^II‐mediated oxidative damage through the formation of an insoluble Cu^II gel which solves the critical challenge of applying Glaser coupling to substrates that are degraded by Cu^II. The generality of this method is illustrated through the conjugation of a series of polar and nonpolar labels onto a fully unprotected GLP‐1R agonist through a linear 7 Å diynyl linker.     

On‐Surface Domino Reactions: Glaser Coupling and Dehydrogenative Coupling of a Biscarboxylic Acid To Form Polymeric Bisacylperoxides

Herein we report the on‐surface oxidative homocoupling of 6,6′‐(1,4‐buta‐1,3‐diynyl)bis(2‐naphthoic acid) (BDNA) via bisacylperoxide formation on different Au substrates. By using this unprecedented dehydrogenative polymerization of a biscarboxylic acid, linear poly‐BDNA with a chain length of over 100 nm was prepared. It is shown that the monomer BDNA can be prepared in situ at the surface via on‐surface Glaser coupling of 6‐ethynyl‐2‐naphthoic acid (ENA). Under the Glaser coupling conditions, BDNA directly undergoes polymerization to give the polymeric peroxide (poly‐BDNA) representing a first example of an on‐surface domino reaction. It is shown that the reaction outcome varies as a function of surface topography (Au(111) or Au(100)) and also of the surface coverage, to give branched polymers, linear polymers, or 2D metal–organic networks.     

Synergistic Effect of NiLDH@YZ Hybrid and Mechanochemical Agitation on Glaser Homocoupling Reaction

Herein, we report the synthesis of nickel-layered double hydroxide amalgamated Y-zeolite (NiLDH@YZ) hybrids and the evaluation of the synergistic effect of various NiLDH@YZ catalysts and mechanochemical agitation on Glaser homocoupling reactions. Nitrogen adsorption-desorption experiments were carried out to estimate the surface area and porosity of NiLDH@YZ hybrids. The basicity and acidity of these hybrids were determined by CO₂-TPD and NH₃-TPD experiments respectively and this portrayed good acid-base bifunctional feature of the catalysts. The NiLDH@YZ-catalyzed mechanochemical Glaser coupling reaction achieved best yield of 83 % for the 0.5NiLDH@0.5YZ hybrid after 60 min of agitation, which revealed the highest acid-base bifunctional feature compared to all the investigated catalysts. The developed catalyst has proven itself as a robust and effective candidate that can successfully be employed up to four catalytic cycles without significant loss in catalytic activity, under optimized reaction conditions. This work demonstrated a new strategy for C−C bond formation enabled by the synergy between mechanochemistry and heterogeneous catalysis.     

后重氮偶合法制备含硝基偶氮苯咔唑类聚合物

后重氮偶合;咔唑;生色团;后重氮偶合法制备含硝基偶氮苯咔唑类聚合物     

Polybinaphthyls of (R)-3,3′-Diiodo-2,2′-binaphtho-20-crown-6 with p-Divinylbenzene via Heck Cross-coupling Reaction

IntroductionFunctional polymers bearing chiral moietiesand the extended conjugatedπ system have attract-ed considerable attention during the pastdecade[1,2 ] .The enantiodifferation properties ofsuch macromolecules give rise to multiple applica-tions in the fields of asymmetric catalysis,chiralsensors,polarized light emission and nonlinear op-tical materials[3 ,4] .Especially the incorporation ofoptically active binaphthyls in the main chain ofconjugated polymers can lead to an efficient ands…     

Organic Polyvalent Iodinc Reagents-Promoted Coupling Reaction of 1-Alkynes

Sincetheearlyl980sinterestin0rganicpoIyvalentiodinec0mp0undshasexperiencedaresurgence'.Afewexamplesofhomo-couplingreacti0nsviathesec0mpoundshavebeenrep0rted-.Wef0undthatl-aIkyneswereeasytoc0upleinthepresenceofPhI(OAc)=orPhI(OH)OTs,catalyticCulandbase,t0aff0rdc0njugateddiynes.l,3-Diyneplaysanimportantr0leinstudiesofm0lecularrec0ngnition',innaturalpr0ducts',andinsynthesis.AlthoughEglintonreaction',Cadi0t-Chalkiewiczc0upling'andGlaserreaction5haveprovidedc0nvenientmeth0dst0synthesizeconjug…