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.     

α-二亚胺钯配合物的合成及催化Suzuki偶联反应

设计合成并表征了3个具有不同骨架结构的α-二亚胺钯配合物,并在有氧条件下催化不同溴代芳烃与芳硼酸的Suzuki偶联反应,重点考察了配合物骨架结构、碱性强度、溶剂极性和不同反应温度对催化反应的影响。结果表明,α-二亚胺类钯配合物能催化Suzuki偶联反应,采用质子溶剂、无机碱,以及较高反应温度都有利于偶联反应的进行,能够高效制备一系列联芳类化合物。     

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.     

环钯化二茂铁亚胺卡宾络合物的合成、表征及其对Buchwald-Hartwig胺化反应的催化性质

合成了一个新的二茂铁亚胺环钯化卡宾络合物, 并经过IR, 1H NMR, 13C NMR, HRMS和X射线衍射对其单晶结构进行鉴定. 新合成的催化剂对空气和湿气都很稳定, 并且对氯代苯参与的Buchwald-Hartwig胺化反应有较好的催化活性, 在摩尔分数为0.5%的催化剂用量下, 3 h即可以达到中等以上的收率.     

环钯化苯基咪唑啉-卡宾络合物的合成及催化Suzuki反应研究

以间硝基苯甲酸或苯甲酸和(S)-缬氨醇为起始原料,室温反应制得酰氨基醇1a和1b,在亚硫酰氯存在下,酰胺基醇与对甲苯胺关环反应得到苯基咪唑啉化合物2a和2b.通过对苯基咪唑啉配体2进行钯化反应、1,3-二苄基苯并咪唑盐解聚,得目标产物环钯化苯基咪唑啉-卡宾络合物3a和3b.通过1H NMR,13C NMR,IR,MS和元素分析等手段对新化合物3a和3b进行了表征.进一步通过单晶X射线衍射对3a进行了结构确证,络合物3a晶体结构表明该化合物通过分子间氢键形成一维链状结构.催化性能考察发现,络合物3a在萘硼酸和碘代甲氧基萘的Suzuki偶联反应中表现出较好的催化活性.     

痕量环钯配合物高效催化合成二茂铁衍生物

选用新型双二茂铁亚胺环钯配合物(Fc2C NPh)Pd Cl PPh3(Fc=Ferrocenyl,Ph=Phenyl)作为催化剂,通过碘代二茂铁作为反应底物,进行Suzuki-Miyaura交叉偶联反应,以良好产率,合成了一系列具有特殊取代基的二茂铁衍生物(1~9).优化了制备二茂铁衍生物的交叉偶联反应条件,考察了底物适应范围,给出了优化合成路线,推测了催化反应机理.结果表明,选用的环钯配合物催化剂对潮气和空气不敏感,具有催化剂用量少(痕量)、催化反应活性高、底物适应范围宽等优点,是制备二茂铁衍生物的理想催化剂.     

环钯化二茂铁亚胺-膦配合物的电喷雾离子阱质谱研究

采用电喷雾离子阱质谱法(ESI-MS)对10种环钯化二茂铁亚胺-膦配合物的质谱特征进行了研究, 获得了其结构碎片信息, 对其质谱裂解途径进行了解析. 结果表明, 在正离子检测方式下可以得到强的准分子离子峰[M-Cl]+簇, 它们的(+) ESI-MSn(n=1~3)质谱主要产生碳-膦键断裂的碎片, 同时也能观察到Pd—P或Pd—C键的断裂, 这些特征为此类化合物及其结构类似物的结构推断提供了依据.     

水溶性亚胺配体/钯催化的室温 Suzuki 反应

 设计并合成了一种新型水溶性亚胺双齿配体 I, 并得到其单晶结构. 该配体具有半配位效应和绿色化学特征, 与氯化钯组成的催化体系在空气和室温条件下, 可有效催化乙醇水溶液中的溴代芳烃与芳基硼酸的 Suzuki 交叉偶联反应. 在 n(ArBr) = 0.5 mmol, n(ArB(OH)₂) = 0.75 mmol, x(PdCl₂) = 1%, x(I) = 2%, n(K₂CO₃) = 1.0 mmol, c(EtOH) = 50% 水溶液的优化条件下, 经 20 min 反应, 分离收率即可达到 99%.     

新型含咔唑双膦配体-钯催化 Suzuki 反应

 以 3-溴苯甲醚为原料合成了新型双膦配体 6,6′-二甲氧基-2,2′-二 (二-N-咔唑基膦)-1,1′联苯, 并将该配体与钯组成的配合物用于对溴苯甲醚和苯硼酸的 Suzuki 偶联反应, 考察了溶剂、碱、底物/催化剂摩尔比、膦/钯摩尔比对偶联反应的影响. 结果表明, 该催化体系在 1,4-二氧六环中催化对溴苯甲醚和苯硼酸的 Suzuki 偶联反应得到 99% 的分离产率. 同时, 该催化体系用于其它芳基溴和苯硼酸的 Suzuki 偶联反应也表现出很好的催化性能, 即使芳基溴有较大的空间位阻或具有取代基也能获得很好的结果.     

Efficient Suzuki coupling of aryl chlorides catalyzed by tricyclohexylphosphine adducts of cyclopalladated ferrocenylimines

The air and moisture stable tricyclohexylphosphine (PCy₃) adducts of dimeric cyclopalladated ferrocenylimines 5 and 6 have been easily synthesized and successfully used in palladium-catalyzed Suzuki cross-coupling of aryl chlorides. Using 0.1 mol% of 6 in the presence of 2 equivalent of Cs₂CO₃ as base in dioxane at 100 °C provided coupled products in excellent yields in the reaction of non-activated and deactivated aryl chlorides with phenylboronic acid. For activated chlorides such as 4-chloronitrobenzene and 4-chloroacetophenone, the catalyst loadings could be lowered to 0.01 mol% without loss of activity.     

Suzuki Coupling Reaction Catalyzed by Cyclopalladated Complexes of Tertiary Arylamines in Ionic Liquid

Suzuki cross-coupling reaction of phenylboronic acid with aryl halides catalyzed by cyclopalladated complexes of tertiary arylamines immobilized in ionic liquid [Bmim]^＋BF4^- was reported. The catalytic system proved to be efficient and be reused at least 3 times without significant loss of activity.     

Water‐Soluble and Recyclable Cyclopalladated Ferrocenylimine for Suzuki Coupling Reaction

A series of new water‐soluble cyclopalladated ferrocenylimines were designed and prepared. They were efficient catalyst for Suzuki coupling reactions of aryl bromides and phenylboronic acid in neat water under ambient atmosphere. Among of these catalysts, the catalyst ( C₂D ) could be reused for 6 times for the Suzuki coupling reaction of 4‐bromotoluene with phenylboronic acid in EtOH/H₂O under ambient atmosphere, in which no significant loss activity of C₂D was observed.     

N-Heterocyclic carbene adducts of cyclopalladated ferrocenylimines: Synthesis,characterization and catalytic activity for the Suzuki–Miyaura reaction

A series of novel air-stable carbene adducts of cyclopalladated ferrocenylimines have been synthesized and characterized. The structures of these complexes were determined by single-crystal X-ray analysis. These adducts have been successfully applied to the Suzuki–Miyaura coupling reaction under aerobic conditions. Good to excellent yields were obtained in short reaction times with a lower loading of the catalyst.     

P,N配位的环钯配合物催化Suzuki偶联合成含氟液晶化合物的研究

合成了P,N配位的环钯配合物1-2.它们不仅是在室温下高效催化对溴甲苯与对氟苯硼酸的交叉偶联反应而且也是合成含氟液晶化合物的高效催化剂.在最佳反应条件下,含氟液晶化合物的产率都超过90%.     

An efficient catalyst for the synthesis of ortho-substituted biaryls by the Suzuki cross-coupling: Triphenylphosphine adduct of cyclopalladated ferrocenylimine

The air and moisture stable triphenylphosphine adduct of cyclopalladated ferrocenylimine 2 has been successfully used in palladium-catalyzed Suzuki cross-coupling for the synthesis of ortho-substituted biaryls in air. In the presence of 0.05 mol% of 2 as catalyst and 3 equivalent of CsF as base in dioxane at 100 °C, ortho-substituted biaryls were synthesized with moderate to high yields in the reactions of 2-methoxy-1-naphthylboronic acid with aryl halides, and 14 new ortho-substituted biaryls were obtained and characterized.     

Fluorogenic derivatization of aryl halides based on the formation of biphenyl by Suzuki coupling reaction with phenylboronic acid

The fluorogenic derivatization method for aryl halide was developed for the first time. This method was based on the formation of fluorescent biphenyl structure by Suzuki coupling reaction between aryl halides and non-fluorescent phenylboronic acid (PBA). We measured the fluorescence spectra of the products obtained by the reaction of p-substituted aryl bromides (i.e., 4-bromobenzonitrile, 4-bromoanisole, 4-bromobenzoic acid ethyl ester and 4-bromotoluene) with PBA in the presence of palladium (II) acetate as a catalyst. The significant fluorescence at excitation maximum wavelength of 275–290 nm and emission maximum wavelength of 315–350 nm was detected in all the tested aryl bromides. This result demonstrated that non-fluorescent aryl bromides could be converted to the fluorescent biphenyl derivatives by the coupling reaction with non-fluorescent PBA. We tried to determine these aryl bromides by HPLC-fluorescence detection with pre-column derivatization. The aryl bromide derivatives were detected on the chromatogram within 30 min without any interfering peak derived from the reagent blank. The detection limits (S/N = 3) for aryl bromides were 13–157 fmol/injection.