二氧化硅负载聚-γ-(二苯胂基)丙基硅氧烷钯(0)配合物的合成与催化卤代芳烃的偶联反应

聚 γ 氯丙基硅氧烷依次与二苯胂钾、氯化钯作用 ,再经水合肼还原 ,合成了二氧化硅负载的聚 γ (二苯胂基 )丙基硅氧烷钯 (0 )配合物 .该钯 (0 )配合物可有效地催化芳基卤化物与烯烃、炔烃、Grignard试剂之间的交叉偶联反应 ,并且可以回收再用多次 ,其活性基本保持不变 .     

二氧化硅负载的聚-4-硫杂-6-二苯膦己基硅氧烷钯(0)配合物的合成与催化性能

聚-4-硫杂-6-二苯膦己基硅氧烷与氯化钯作用后经水合肼还原,合成了二氧化硅负载的硫-膦混合双齿钯(0)配合物.该配合物可以有效地催化芳(烯)基卤化物与烯烃、炔烃、Grignard试剂的交叉偶联反应,并可回收多次利用,活性基本不变.     

聚γ-(p-二苯膦苯基)丙基硅氧烷钯(Ⅱ)配合物的合成及其催化羰基化性能

负载型催化剂;膦钯配合物;聚γ-(p-二苯膦苯基)丙基硅氧烷钯(Ⅱ)配合物的合成及其催化羰基化性能     

有机硅聚合物负载环硫乙烷钯(0)配合物的合成与催化性能

４ 氧杂 ６ ,７ 环硫庚基三甲氧基硅烷依次与气相法二氧化硅、氯化钯作用,再用水合肼还原,合成了二氧化硅固载的聚４ 氧杂 ６ ,７ 环硫庚基硅氧烷钯（０） 配合物,研究了其催化共轭烯烃的 Ｈｅｃｋ 芳基化性能     

壳聚糖钯(0)配合物催化Heck芳基化反应研究

以天然高分子壳聚糖为载体,室温下通过与氯化钯乙醇溶液作用制得壳聚糖负载氯化钯黄色粉末,再在乙醇溶液中回流还原,制得了壳聚糖钯(0)配合物催化剂,研究了其对碘代苯与丙烯酸Heck芳基化反应的催化性能.结果表明该催化剂具有较高的催化活性和立体选择性,可高转化率、高产率地合成反式苯丙烯酸;通过简单的过滤、溶剂洗涤回收催化剂,并能多次重复使用.该催化剂对其它反应底物的催化性能也进行了探讨.     

聚-ω-(甲硒基)十一烷基硅氧烷钯(0)配合物的合成与催化性能

ω-氯代十一烷基三乙氧基硅烷依次用气相法二氧化硅固载、与甲硒基钠和氯化钯作用,再用水合肼还原,合成了气相法二氧化硅负载的聚-ω-(甲硒基)十一烷基硅氧烷钯(0)配合物.该钯(0)配合物对丙烯腈和丙烯酸与芳基碘的Heck芳基化反应具有很高的催化活性,为各种肉桂腈和肉桂酸的立体选择合成提供了方便实用的新途径.     

聚-ω-(甲硒基)十一烷基硅氧烷钯(0)配合物的合成与催化性能

ω-氯代十一烷基三乙氧基硅烷依次用气相法二氧化硅固载、与甲硒基钠和氯化钯作用, 再用水合肼还原, 合成了气相法二氧化硅负载的聚-ω-(甲硒基)十一烷基硅氧烷钯(0)配合物. 该钯(0)配合物对丙烯腈和丙烯酸与芳基碘的Heck芳基化反应具有很高的催化活性, 为各种肉桂腈和肉桂酸的立体选择合成提供了方便实用的新途径.     

细胞色素P-450模拟体系的活性中间体—亚碘酰苯铬(Ⅳ)四苯基卟啉配合物的分离、表征和氧化反应

铬(Ⅲ)四苯基卟啉-亚碘酰苯体系在温和条件下能催化氧化碳氢化合物,是细胞色素P-450很好的模拟体系。分离和表征细胞色素P-450模拟体系的活性中间体,不仅能解释细胞色素P-450模拟体系催化氧化碳氢化合物的反应机理,而且也有助于深入了解细胞色素P-450催化氧化碳氢化合物的反应机理及其活性中间体的结构。我们首先分离和表征的细胞色素P-450模拟体系的一种活性中间体-氧配位铬(V)四苯基卟啉配合物,具有氧化碳氢化合物的活性。这篇论文报道细胞色素P-450模拟体系的另一种活性中间体-亚碘酰苯铬(Ⅳ)四苯基卟啉配合物的分离,表征和对环已烯的氧化性质。     

混合配体配合物钯(Ⅱ)-联喹啉-苯乙基丙二酸根与DNA作用研究

The mixed ligand complex [Pd(biqu)(pmal)]·H₂O (where biqu is 2,2′-biquinoline, pmal is phenethylmalonate) has been synthesized and its interaction with sperm DNA was determined by fluorescent spectra、 UV-Vis spectra and CD-spectra. The binding constant (K_b) of the complex and sperm DNA is 1.26×10⁴ and its interaction with pBR322 plasmid DNA was also determined by gel electrophoresis. The results show that the complex interact with DNA mainly by intercalative mode.     

有机硅聚合物负载硫、腈钯(0)配合物催化丙烯酸衍生物芳基化的研究

钯催化下共轭烯烃的Ｈｅｃｋ芳基化是立体选择性形成碳碳键的重要方法,在有机合成中广为应用［１］．均相钯催化剂因难以从反应体系中分离回收,其实际应用受到限制．聚合物负载过渡金属催化剂因综合了均相和复相催化过程的优势,已越来越引起人们的关注,聚苯乙烯负载的膦钯配合物能有效地催化共轭烯烃的芳基化［２,３］．Ｚｈａｎｇ等报道了聚合物负载菲咯啉钯（０）配合物催化丙烯酰胺的芳基化［４］,但该催化剂的制备过程过于复杂．作者曾报道过聚γ巯丙基硅氧烷钯（０）配合物的合成,并证实其是苯乙烯、丙烯酸Ｈｅｃｋ芳基化反…     

Heck Arylation of Acrylonitrile with Aryl Iodides Catalyzed by a Silica-bound Arsine Palladium(0) Complex

The palladium-catalyzed arylation of alkenes is an important discovery in organo-palladium chemistry made by Heck et al. and has found wide application in organicsynthesis1,2. In this reaction, homogeneous palladium complexes such as Pd(OAc)2 areusually used as the catalysts and the amount of catalyst used is about 2 mol% of reactant.Although homogeneous palladium catalysts have proven to be efficient, their activity andstereoselectivity are moderate and use of homogeneous palladium catalysts…     

Silica-Supported Phosphine Palladium(0) Complex Catalyzed Phenylation of Acid Chlorides and Aryl Iodides by Sodium Tetraphenylborate

In the presence of a catalytic amount of silica – supported phosphine palladium(0) complex, sodium tetraphenylborate (NaBPh₄) reacts with acid chlorides under mild conditions to give the corresponding phenyl ketones in 57 – 80% yields; it also reacts with aryl iodides to afford the corresponding biaryls in 75 – 84% yields.     

二氧化硅负载的胂钯(0)配合物作为丙烯酸丁酯和丙烯酰胺芳基化反应高活性和高立体选择性的催化剂

A silica-supported arsine palladium(O) complex has been prepared from y-chloropropyltriethoxysilane via immobilization on fumed silica, followed by reaction with potassium diphenylarsenide and palladium chloride, and then reduction with hydrazine hydrate. The complex has been characterized by X-ray photoelectron spectroscopy (XPS) and it is a highly active and stereoselective catalyst for arylation of butyl acrylate and acrylamide with aryl halides, affording a variety of tram-butyl cinnamates and trans-cinnamamides in high yields.     

Arylation of Allylic Alcohols with Aryl Iodides Catalyzed by a Silica-Bound Bidentate Sulfur Palladium (0) Complex

Thepalladium-catalyzedarylation0fallylicalc0h0lswitharylhalideshaspr0videdaconvenientmethodforthesynthesisof3-arylaldehydesandket0nesl'2.Benhaddouetal.3havestudiedthekineticsofthisarylationreaction.H0wever,homogene0uspalladiumcatalystssuchasPd(0Ac)2andPdCl2areusuallyused,anditisdifficulttorecuverthemfromthereactionmixture.ThemethodofinunobilizingcomPlexeshasmadehomogeneouscatalystsgenerallymoreattractivefromtheoreticalandindustrialpointsofview.Polymer-supportedpalladiumcatalystshavebeensucce…     

一种经MCM-41负载双齿膦钯(0)配合物催化的羰基化Suzuki偶联合成二芳酮的新途径

在催化量的MCM-41负载双齿膦钯(0)配合物存在下,芳基碘化物和芳基硼酸、一氧化碳在常压下能顺利进行羰基化Suzuki偶联反应,高产率地生成了各种二芳酮化合物。MCM-41负载双齿膦钯(0)配合物具有比PdCl2(PPh3)2 更高的活性和选择性,且可回收再用10次其活性基本不变,为各种功能化二芳酮的合成提供了方便实用的新途径。     

Cross—Coupling of Aryl Iodides with Malononitrile Catalyzed by Palladium N—Heterocyclic Carbene Complex System

Eight N-heterocyclic carbenes (NHC),generated in situ from their imidazolium salts,as ligands of palladium complexes were used for the catalytic coupling of iodobenzene with malononi-trile anion,It was found that 1,3-bis(2,4,6-trimethylphenyl)-imidazolium chloride (IMesHCl)-Pd2(dba)3 catalytic system has the highest activity to obtain phenyl malononitrile among the imidazolium salts.The substituted iodoarenes reacted with malononitrile anions by using the catalytic system to give cross-coupling products in yields from 50% to 96%.     

聚-4-氧杂-6,7-二甲硒基庚基硅氧烷钯(0)配合物的合成及其催化性能研究

4 氧杂 6,7 二氯庚基三甲氧基硅烷依次与气相法二氧化硅、甲硒基钠、氯化钯作用 ,然后用水合肼还原 ,合成了二氧化硅负载的聚 4 氧杂 6,7 二甲硒基庚基硅氧烷钯 ( 0 )配合物 .该配合物是苯乙烯及丙烯酸的Heck芳基化反应的有效催化剂 ,为立体选择性地合成各种取代的反式 1,2 二苯乙烯及反式肉桂酸提供了简便且实用的新方法 .