含有酯基二茂铁亚胺环钯化合物催化Suzuki和Heck反应

合成并表征了系列含有酯基二茂铁亚胺环钯化合物.结果表明,该系列环钯催化剂在纯水或有机溶剂中均能高效催化Heck和Suzuki偶联反应.     

含杂环二茂铁亚胺异环环钯化合物在Heck反应中的催化活性研究

含杂环二茂铁亚胺异环环钯化合物结构新颖、独特,其催化的Heck偶联反应具有底物范围广、反应条件温和、催化活性高且催化诱导期短等优点。芳基碘代物、芳基溴代物和芳基氯代物都可作为反应底物,其中化合物2应用于芳基溴代物和丙烯酸乙酯的反应得到了100%的收率。在反应中加入四丁基溴化铵,且提高反应温度到140℃,带有斥电子取代基的芳基溴代物、芳基氯代物仍能以较高的产率得到偶联产物。实验中利用薄层色谱监测反应。     

钯催化二茂铁硼酸和有机三氟甲磺酸酯制备单取代二茂铁芳基化合物的偶联反应

在Pd(PPh3)4催化下,以K3PO4为碱,以二氧六环为溶剂,二茂铁硼酸和有机三氟甲磺酸酯在回流条件下高收率得到了单取代二茂铁的偶联产物.不同三氟甲磺酸酯的偶联反应产率在72%～92%之间.     

平面手性二茂铁亚胺环钯、环汞化合物与金属锡的 金属转移反应

通过手性二茂铁亚胺环钯化合物(Sp,Sp)-[{Pd[(η^5-C~5H~5)Fe{(η^5-C~5H~3)C(CH~3)＝N-Ar}](μ-Cl)}~2],手性二茂铁亚胺环汞化合物[HgCl{η^5-C~5H~5)Fe(η^5-C~5H~3)C(CH~3)＝N-Ar}]与金属锡的金属转移反应,均得到保持茂环平面手性的手性二茂铁亚胺环锡化合物。产物均经元素分析、IR和^1HNMR鉴定,X射线晶体结构分析确定了有机锡化合物的绝对构型,并经CD谱验证。     

二茂铁亚胺环钯化合物催化的带有导向基团的sp2C-H键底物的邻位芳基化

发展了一种以二茂铁亚胺环钯化合物为催化剂, 对带有导向基团的sp2 C—H键芳基底物进行邻位芳基化的新颖高效的催化体系. 实验结果表明, 反应表现出明显的区域选择性, 芳基化只发生在空间位阻较小的sp2 C—H键上, 反应可以采用多种取代基(如CH3O, CH3CO, Br和Cl)进行, 这有助于通过进一步反应构建更为复杂的新化合物.     

二茂铁亚胺环钯化合物在Heck反应中的催化活性研究

二茂铁亚胺环钯化合物1和2催化Heck反应具有底物范围广、反应条件温和、不需要惰性气体保护、催化活性高、重复使用仍能保持活性的特点。芳基碘化物、溴化物和氯化物都可为反应底物。化合物2应用于碘苯和丙烯酸西酯的反应得到了92%的产率和7360000的转化数;应用于碘苯和丙烯酸乙酯的偶联反应,反复使用五次仍然保持很高的活性。利用高压液相色谱或薄层色谱监测反应。     

由二茂铁亚胺环钯催化的Suzuki偶联反应合成具有发光性能的3-芳基噻吩

3-芳基取代噻吩大多是电致发光材料的前体化合物. 催化剂摩尔分数为0.5% 的二茂铁亚胺环钯化合物在DMF/K3PO4/80 ℃条件下, 能够有效地催化3-噻吩硼酸同芳基碘和芳基溴的Suzuki反应, 方便地合成系列3-芳基噻吩衍生物. 此方法操作简便, 不需要加入过量的3-噻吩硼酸, 催化剂用量小. 化合物3b, 3c和3d的发射光谱和激发光谱表明, 此类化合物具有潜在的发光应用性能.     

新型手性二茂铁腙类环钯化合物的合成及其晶体结构

手性二茂铁腙类环钯化合物[(+)-(S)-2-(甲氧基甲基吡咯烷-1-基)-1-乙酰基二茂铁亚胺]在甲醇中与Pd(OAc)2和AcONa·3H2O经不对称环钯化反应合成了两个新型的双-醋酸桥环钯衍生物[syn-(+)-(Rp,S,S,Rp)-3和syn-(+)-(Sp,S,S,Sp)-3];syn-(+)-(Rp,S,S,Rp)-3或syn-(+)-(Sp,S,S,Sp)-3在甲醇中与NaNO2反应合成了两个新型的双亚硝酸桥平面手性环钯化合物[syn-(+)-(Rp,S,S,Rp)-4和syn-(+)-(Sp,S,S,Sp)-4],其结构经1H NMR,元素分析和X-单晶衍射表征。     

壳聚糖亚胺环钯化合物的合成及其催化性能研究

壳聚糖与苯甲醛或其衍生物作用制得壳聚糖席夫碱, 再与氯化钯锂的甲醇溶液作用, 制得壳聚糖亚胺环钯催化剂. 该类催化剂对空气和水稳定, 对于苯乙烯与芳基碘的交叉偶联反应具有较高的催化活性和选择性, 经简单分离回收可重复使用多次. 为立体选择性合成各种取代的1,2-二苯乙烯提供了一种制备简单、实用的高活性绿色催化剂体系.     

缬氨醇衍生的手性二茂铁亚胺环钯化合物的合成及晶体结构

含氮配位基团的二茂铁衍生物的环钯化合物在有机合成、催化等领或有着重要的应用,尽管目前已经合成了从多的二茂铁环钯化合物,但其中绝大部分为外消旋体。二茂铁是引入平面手性的理想骨架,通过经典的拆分方法或利用光学纯的二茂铁配体进行不对称环钯化反应可得到具有平面手性的二茂铁环钯化合物,研究发现,利用平面手性的二茂铁环钯化合物与金属汞嘲、锡等的金属转移反应可方便地制备平面构型保持的手性环汞、环锡化合物;还可将它们用于外消旋氨基酸的手性拆分及催化不对称Claisen重排反应（ee值最高可达95％）。     

Cyclopalladated Ferrocenylimine Catalyzed Chlorination of 2‐Arylbenzoxazoles

An efficient and facile protocol for palladacycle‐catalyzed chlorination of 2‐arylbenzoxazoles was developed. The results represent the first examples involving the palladacycle as the catalyst for such chlorination. This chlorination was not a ligand‐directed ortho‐C H activation, but an electrophilic substitution process at the para‐position of the nitrogen atom in the benzo ring of benzoxazole moiety, the regiochemistry of which had been confirmed by HMBC spectral analysis. The catalytic system could tolerate various halogen atoms, such as F, Cl and Br, affording the corresponding products in moderate to excellent yields.     

Cyclopalladated ferrocenylimine as an efficient catalyst for the syntheses of diarylmethane derivatives

The cyclopalladated ferrocenylimine adducts Ia , Ib , Ic were evaluated in the Suzuki cross‐coupling reaction of benzyl halides with arylboronic acids. The tricyclohexylphosphine adduct Ia exhibited highly catalytic activity for the coupling of aryl and heteroaryl boronic acids containing various functional groups with benzylic bromides and chlorides (up to 99% yield), furnishing diarylmethane derivatives with low catalyst loading (1 mol%). It is worth noting that catalyst Ia can be reused eight times without losing its catalytic activity. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and Structures of New Cyclopalladated Ferrocenylimines

The chemistry of cyclopalladated compounds has been of general interest for decades, due to their various applications in organic and organometallic synthesis, material science, catalysis and photochemistry, in particular those containing nitrogen and (Pd…     

PVP-Supported Palladium-Cadmium Bimetallic Catalyst for the Hydrogen Transfer Dechlorination of Aryl Chlorides

SupportedbimetalIiccatalysts,duet0theirhighselectivityandcatalyticactivity,havebeenxvidelyappliedtothehydrogenationofnitro-compounds'andesters',thecarb0n}lIati0n0fallylhalides'andthecatalytichydrodehalogenati0nofaromatichalides;'.LiaoandothersutilizedPVP[PVP=poly-(N-vinyl-2-pyrrolidone)]-supp0rtpaIladium-rutheniUm'andpalladium-c0balt'bimetalliccatalysts,inthepresence0fdihydrogen,tocatalyzethehydr0dechl0rinati0n0farylchl0rides.Alth0ughthesereacti0nshadhighcatalyticactivity,the0perati0nwasra…     

Alkylsulfamoyl Chlorides as Key Units in the Synthesis of Novel Biologically Active Compounds for Crop Protection

Due to their bifunctional character, alkylsulfamoyl chlorides are versatile units for the synthesis of heterocycles, polar sulfamates, and sulfonamides. In the last decade, synthetic methods of general preparative use have been developed, by means of which amine hydrochlorides, isocyanates, aziridines or tertiary alcohols can be reacted with suitable sulfuric acid derivatives to give novel, variously substituted alkylsulfamoyl chlorides. These compounds can subsequently be converted either to previously unobtainable N-alkoxyalkyl-N-alkylsulfamoyl chlorides or to novel heterocycles of the type 1H-2,1,3-benzothiadiazin-4-one-2,2-dioxide, 2H-1,2,6-thiadia-zin-3-one-1,1-dioxide and 2H-1,2,4,6-thiatriazin-5-one-1,1-dioxide; these compounds are examples of interesting models which illustrate the relation between the structure and the action of the compound, and in some cases lead to highly selective, ecologically unobjectionable herbicides. On the other hand, the alkylsulfamoyl chlorides themselves can be N-acylated to give further 3- to 5-atom bifunctional synthesis units, with which novel heterocyclic syntheses can be carried out. Further uses of the alkylsulfamoyl chlorides include the preparation of biologically active sulfamates, and cycloaddition reactions of N-sulfonylamines prepared in situ.     

First palladium‐catalyzed denitrated coupling reaction of nitroarenes with phenols

The first palladium‐catalyzed protocol for the denitrated coupling reaction of nitroarenes with phenols has been developed, achieving unsymmetrical diaryl ethers in moderate to excellent yields. The cyclopalladated ferrocenylimine (catalyst Ic ) exhibited highly catalytic activity for this transformation with low catalyst loading (0.75 mol%) and short reaction time (2 h). The efficiency of this reaction was demonstrated by its compatibility with a range of groups. Moreover, the rigorous exclusion of air or moisture was not required in these transformations. Copyright © 2013 John Wiley & Sons, Ltd.     

Homocoupling of Aryl Iodides Catalyzed by Cyclopalladated Complexes of Tertiary Arylamines

Homocoupling of aryl iodides catalyzed by cyclopalladated complexes of tertiary arylamines gives symmetric biaryls with good yields in DMA or ionic liquid [Bmim]BF4. This catalytic alternative of the Ullmann reaction has proved to be sensitive to both electronic and steric factors of substrates.     

异丁烯二聚反应

由于甲基叔丁基醚(MTBE)对水源的污染,它作为汽油添加剂的应用受到环保限制,并对其生产和应用前景带来消极影响。MTBE经裂解、二聚和加氢生产异辛烷成为国外现有MTBE装置转产的主要途径。本文对异丁烯二聚催化剂、反应活性位、机理及动力学研究成果进行了综述,试图解释在异丁烯二聚时,加入的叔丁醇对二聚反应选择性提高的作用机理,为今后二聚反应的研究提供参考。     

环钯化二茂铁亚胺-三苯基膦配合物的合成、表征及催化Suzuki反应研究

为筛选高效催化Suzuki反应的催化剂, 合成了3种新的环钯化二茂铁亚胺-三苯基膦配合物2~4, 经元素分析(或HRMS)、 红外光谱和核磁共振谱对其结构进行了表征, 并通过X射线单晶衍射测定了化合物3的晶体结构. 这些化合物容易合成, 在空气和溶液中稳定, 可用作芳基溴及杂芳基溴与苯基硼酸偶联的Suzuki反应催化剂. 使用摩尔分数为0.01%的催化剂3, 以2倍量的K3PO4为碱, 于110 ℃下, 在甲苯中反应5~15 h, 使具有不同电子和位阻效应的取代芳基溴及杂芳基溴能以较高的产率与苯基硼酸反应生成偶联产物; 与溴苯相比, 带吸电子基的溴苯反应活性较高, 催化剂的摩尔分数降低至0.001%时, 仍能得到较高产率, 而带强给电子基的溴苯如4-溴苯甲醚及带邻位取代基的溴苯在其它条件相同时, 需要延长反应时间才能得到较高的产率.     

官能化硅胶负载Pd—Cu催化剂的制备及催化芳香氯化物水相脱氯作用

将聚乙烯吡烷酮（PVP）与双金属Pd^2 、Cu^2 配位后,再负载于用平均分子量为600的聚乙二醇（PEG）官能化的硅胶上（SiO2-PEG600),制成一种新型双负载双金属催化剂PVP-PdCl2-CuCl2/SiO2-PEG600,将其用于催化难溶于水的芳香卤化物水相脱卤,在无需加入任何有机溶剂的情况下,对芳香氯化物呈现出高的脱氯活性和选择性,并具有良好的重复使用性能。通过IR、TEM、比表面积测定等手段,探讨了催化剂各组分在催化脱卤中的作用及可能的催化脱卤机理。