环钯化合物在Heck反应中的应用研究

钯催化交叉偶联反应在化学工业、合成天然产物及生物活性物质中有着广泛的应用.催化剂体系是交叉偶联反应研究的核心.环钯化合物结构简单、性能稳定,在催化交叉偶联反应中具有高活性、高选择性,引起研究者们的极大关注,不断有新的环钯化合物被合成出来,其催化性能也得到了研究.本文综述了环钯化合物的合成方法及其在Heck反应中的应用.     

双齿有机膦二茂铁钯(II)配合物的合成和催化活性

以1,1'-双(二苯基膦)二茂铁(dppf)、1,1'-双(二叔丁基膦)二茂铁(dtbpf)为配体,合成了一类双齿有机膦二茂铁钯(Ⅱ)配合物[(dppf)PdCl_2]、[(dtbpf)PdCl_2]、[(dppf)PdBr_2]和[(dtbpf)PdBr_2],通过核磁共振对配合物进行化学结构表征。评价了它们对Suzuki偶联反应、Sonogashira偶联反应、Heck偶联反应以及2-羟基吡啶与硼酸试剂之间的偶联反应的催化作用。结果表明,配合物化学性质稳定,在非保护气氛下能高效地催化一系列偶联反应。催化剂在单边Sonogashira偶联反应中不但具有较高的催化活性,而且有很好的选择性,显示出很好的应用前景。     

环钯化合物在Heck反应中的应用研究

钯催化交叉偶联反应在化学工业、合成天然产物及生物活性物质中有着广泛的应用.催化剂体系是交叉偶联反应研究的核心.环钯化合物结构简单、性能稳定,在催化交叉偶联反应中具有高活性、高选择性,引起研究者们的极大关注,不断有新的环钯化合物被合成出来,其催化性能也得到了研究.本文综述了环钯化合物的合成方法及其在Heck反应中的应用.     

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.     

环钯化合物在Heck反应中的应用研究

钯催化交叉偶联反应在化学工业、合成天然产物及生物活性物质中有着广泛的应用。催化剂体系是交叉偶联反应研究的核心。环钯化合物结构简单、性能稳定,在催化交叉偶联反应中具有高活性、高选择性,引起研究者们的极大关注,不断有新的环钯化合物被合成出来,其催化性能也得到了研究。本文综述了环钯化合物的合成方法及其在Heck反应中的应用。     

N-环钯化二茂铁衍生物的合成和应用（英文）

近年研究表明二茂铁的环钯化衍生物被广泛地应用于各类偶联反应中,比如Heck反应、Suzuki反应、aza-Claisen重排反应等.主要综述了含氮导向基的二茂铁衍生物的环钯化反应,包括通过不对称诱导或拆分手段合成具有平面手性环钯化合物,基于环金属化反应1,1'-取代二茂铁钯化物的合成,以及其在催化反应的应用.     

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%.     

(聚酰胺-胺)-水杨醛席夫碱树枝状大分子钯配合物的合成、表征及催化性能

首先通过发散法合成出1.0G～5.0G聚酰胺-胺树枝状大分子PAMAM;然后利用氨基与醛的脱水缩合反应,用水杨醛对大分子进行修饰合成出(聚酰胺-胺)-水杨醛席夫碱树枝状大分子配体PAMAMSA;再通过PAMAMSA与氯钯酸锂在甲醇中反应制得一系列钯配合物PAMAMSA-Pd.用红外光谱、核磁共振谱、热重-差热法对所合成的材料结构组成进行了表征与确证.研究了在纯水介质中PAMAMSA-Pd作为催化剂前躯体对碘代苯及其衍生物与丙烯酸Heck交叉偶联反应的催化性能,并比较了钯配合物和PdCl2的催化活性,结果表明树枝状大分子催化剂显示出良好的催化活性,其中1.0G PAMAMSA-Pd和5.0G PAMAMSA-Pd的活性较高.     

金催化的环化反应与钯催化的炔醇偶联/环化反应相结合用于合成多取代呋喃衍生物:串联反应的应用范围(英文)

开发了一种由金和钯催化π-活化由炔醇合成呋喃衍生物的集成方法.该合成策略是最显著的特点适用于带环辛基的底物,其适用范围比之前报道的有很大扩展.在Sonogashira反应条件下,由相应底物可直接得到环辛基呋喃.Pd在这些反应中起到2个重要作用:底物发生偶联反应的关键催化剂;通过π-活化促进炔醇中间体成环反应.该方法在一步合成3-碘呋喃反应中作用很突出,使通过偶联法进一步官能团化成为可能.我们还将AuBr_3用于多米诺成环/C-H键活化反应和无环前体的成环反应.本文结果表明,在该类成环反应中金和钯催化剂相辅相成.     

P⌒O环钯配合物的合成及对Suzuki交叉偶联反应的催化性能

P⌒O环钯配合物的合成及对Suzuki交叉偶联反应的催化性能;合成;二苯基膦丙酸钠;Suzuki偶联反应     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.