1-芳基-3-芳甲酰基中氮茚的合成

合成了九个1-芳基中氮茚衍生物。首先由取代苯乙酮,碘,乙酸和吡啶四组分一锅煮反应合成中间体1-碘代中氮茚,然后在钯催化剂作用下,使用制得的的1-碘代中氮茚和芳基硼酸的Suzuki偶联反应合成得到目标化合物,所合成化合物结构通过红外,核磁及质谱进行了表征。     

1-芳乙炔基-3-芳甲酰基中氮茚的合成研究

设计合成了七个具有炔基的中氮茚衍生物。首先由取代苯乙酮,碘,乙酸和吡啶四组分一锅煮反应合成中间体1-碘代中氮茚,然后在钯催化剂作用下,1-碘代中氮茚和芳基乙炔发生Sonogashira偶联反应合成目标化合物,结构通过红外、核磁及质谱进行了表征。     

Pd(Ⅱ)催化1,4-二苯基-1,3-丁二炔的合成

以苯乙炔为原料制备1,4-二苯基-1,3-丁二炔。以钯催化自偶联的方法合成对称性芳基丁二炔,通过优化碱、溶剂、反应时间和温度等条件得出最优反应条件。结果表明,采用最优条件,在2 mmol Ag NO3促进作用下,1,4-二苯基-1,3-丁二炔的产率达84.3%。     

Pd(Ⅱ)催化1,4-二苯基-1,3-丁二炔的合成

以苯乙炔为原料制备1,4-二苯基-1,3-丁二炔。以钯催化自偶联的方法合成对称性芳基丁二炔,通过优化碱、溶剂、反应时间和温度等条件得出最优反应条件。结果表明,采用最优条件,在2 mmol Ag NO3促进作用下,1,4-二苯基-1,3-丁二炔的产率达84.3%。     

钯催化一锅法合成2-碘联芳烃的研究

Suzuki偶联反应是构建分子碳骨架的有效手段之一,因而被广泛应用于联芳烃化合物的合成,长期以来受到化学家们的广泛关注。本文通过两步一锅法钯催化芳基硼酸与2-碘苯胺发生Suzuki偶联反应,生成的2-氨基联苯不用分离发生重氮化反应直接转化为2-碘联芳烃化合物。该方法无需磷配体的参与,催化剂的用量较低,合成产率进一步提高,操作更加简单易行。     

芳基硼酸在有机合成中的应用

芳基硼酸作为一种重要的中间体,在有机合成中的应用相当广泛。Suzuki偶联反应是合成联芳基结构最有效的方法之一,近年许多用于芳基硼酸与各种卤代芳烃偶合的催化剂相继被开发。芳基硼酸与苯酚在Cu(OAc)2和NEt3存在时用于合成二芳基醚,与胺的偶联是合成C-N键的有效方法,与,α-β不饱和体系的1,4-共轭加成反应广泛用于β-取代羰基化合物的合成。反应采用相对无毒而又廉价的普通试剂,反应条件温和,产率高,立体选择性好。综述了芳基硼酸在联芳基合成、二芳基醚合成、芳香胺合成和催化加成反应中的应用。     

超声辐射下的C-C偶联反应

在四(三苯基膦)钯的催化下,单芳基硼酸和溴代芳烃在超声波作用下发生C-C偶联反应,较快地生成了二芳基化合物-联苯,并研究了反应时间的影响。     

MCM-41分子筛固载羧基钯（Ⅱ）配合物催化剂的制备、表征和催化性能(Ⅱ)催化Heck偶联反应性能

合成了一系列新的MCM-41分子筛固载羧基钯(Ⅱ)配合物, 并研究了其催化碘代芳烃与共轭烯烃的Heck偶联反应的性能以及反应温度、溶剂和碱试剂对催化性能的影响。结果表明,MCM-41分子筛固载双羧基钯(Ⅱ)配合物对催化Heck偶联反应具有高的活性、立体选择性和稳定性,在Et3N-DMF或Bu3N-DMF溶剂体系中,在70℃下7 h内可高产率地合成一系列取代的反式偶联产物,其催化性能明显优于无定形SiO2固载的羧基钯(Ⅱ)配合物,而且表面双羧基改性的催化性能也优于单羧基改性的催化剂。     

水溶性3-(2-二苯基膦-苄氧基)-丙烷-1-磺酸钠新配体/钯催化Suzuki反应研究

设计并合成了一种新型水溶性3-(2-二苯基膦-苄氧基)-丙烷-1-磺酸钠配体并进行了结构表征,该配体与四氯钯酸钾组成的催化剂在水中和微波协助下可有效催化芳基卤代烃和芳基硼酸的交叉偶联反应。在最佳的反应条件:N,N-二甲基甲酰胺/水(体积比3∶2)做溶剂,氢氧化钾做碱,微波120℃反应10min,相应的分离产率可以到达83%~97%,氯代芳烃也有较好的偶联产物。     

二茂铁烯丙基卡宾钯络合物的合成及催化性能

采用一锅法将咪唑盐对二茂铁烯丙基钯二聚体I在室温下进行解聚，避免了使用不稳定的卡宾，简便、高效地合成了二茂铁烯丙基卡宾钯络合物II。通过IR，1H NMR，13C NMR，MS，HRMS和X射线单晶衍射对其结构进行鉴定。络合物II对空气和湿气稳定，且对芳基氯代物参与的Suzuki-Miyaura 偶联反应和Buchwald-Hartwig胺化反应展现较高的催化活性。在反应温度70 oC，0.4 mol％络合物II催化芳基氯代物与芳基硼酸的偶联反应时，取得95-100%收率；在反应温度100 oC，0.5 mol％钯络合物II催化氯苯与多样化胺的偶联反应时，也获得中等至好的的收率。     

Oxime‐Derived Palladium Complexes as Very Efficient Catalysts for the Heck–Mizoroki Reaction

Oxime‐derived, chloro‐bridged palladacycles 16 are efficient complexes for the Heck vinylation of aryl halides. The isolated catalysts are thermally stable, not sensitive to air or moisture and easily accessible from inexpensive starting materials. The reaction can be performed under aerobic conditions, with aryl iodides, bromides and chlorides with acrylic esters and olefins displaying turnover numbers (TON) of up to 10¹⁰ for phenyl iodide and turnover frequencies (TOF) of 1.4×10⁸ h⁻¹. Deactivated aryl bromides undergo the Heck reaction with styrene with TON and TOF values up to 97,000 and 6063 h⁻¹, respectively. Even aryl chlorides undergo the coupling reaction with olefins with TON up to 920. Complexes 16 catalyze the synthesis of 2,3‐disubstituted indenones and indoles in good yields via annulation reaction of internal alkynes with o‐bromo‐ or o‐chlorobenzaldehyde and o‐iodoaniline, respectively.     

An Amine‐, Copper‐ and Phosphine‐Free Sonogashira Coupling Reaction Catalyzed by Immobilization of Palladium in Organic–Inorganic Hybrid Materials

An immobilization of palladium in organic‐inorganic hybrid materials‐catalyzed Sonogashira coupling reaction has been described. Terminal alkynes reacted with aryl iodides and aryl bromides only in the presence of a 3‐(2‐aminoethylamino)propyl‐functionalized, silica gel‐immobilized palladium catalyst under amine‐, copper‐ and phosphine‐free reaction conditions. The reaction generates the corresponding cross‐coupling products in excellent yields. Furthermore, the silica‐supported palladium can be recovered and recycled by a simple filtration of the reaction solution and used for 30 consecutive trials without any decreases in activity.     

Palladium‐Catalyzed Fluoride‐Free Cross‐Coupling of Intramolecularly Activated Alkenylsilanes and Alkenylgermanes: Synthesis of Tamoxifen as a Synthetic Application

We have demonstrated that intramolecular hypercoordination of a carboxylic acid is a powerful activation strategy for the palladium‐catalyzed cross‐coupling reaction of trialkyl(vinyl)silanes and trialkyl(vinyl)germanes under fluoride‐free conditions. Z‐β‐Trialkylsilyl‐ and Z‐β‐trialkylgermylacrylic acids, synthesized stereoselectively by olefination with ynolates, are highly stable and useful reagents for cross‐coupling with a variety of aryl iodides to provide tetrasubstituted olefins possessing different carbon substituents in a stereocontrolled and diversity‐oriented manner. An application to a stereoselective synthesis of (Z)‐tamoxifen is also reported.     

High-turnover aminopyridine-based Pd-catalysts for Suzuki–Miyaura reaction in aqueous media

A high-turnover catalytic system based on commercially available aminopyridines (L) and PdCl₂ has been developed for Suzuki–Miyaura reaction in aqueous media. Reactions of arylboronic acids with a wide range of aryl iodides, bromides and chlorides proceeded in the presence of these catalysts for a short time in aqueous media to afford the cross-coupling products in high yields. Furthermore, this protocol allows tolerating a wide range of functional groups.     

Synthesis of 1,4‐Diarylbuta‐1,3‐dienes through Palladium‐ Catalyzed Decarboxylative Coupling of Unsaturated Carboxylic Acids

It has been found that readily available hydroxylated cinnamic acids such as ferulic acid undergo palladium‐catalyzed decarboxylative coupling with aryl iodides and internal alkynes in a 1:1:1 manner to produce 1,4‐diarylbuta‐1,3‐dienes. The butadiene synthesis has also been achieved through the coupling of aryl halides with dienoic acids. Some of the products exhibit solid‐state fluorescence.     

An efficient and recyclable thermoregulated phosphine–palladium catalyst for the carbonylative Suzuki coupling of aryl halides with arylboronic acids in water

An efficient protocol has been developed for the carbonylative Suzuki coupling of aryl halides using the thermoregulated phosphine–palladium as a reusable catalyst in pure water. This protocol was applied to a wide variety of hindered and functionalized aryl iodides and bromides with arylboronic acids, to afford the desired biaryl ketones in good to high yields. The palladium catalyst was easily recovered in the aqueous phase and reused up to eight cycles without a significant decrease in its activity.     

An efficient LDH-Pd0-catalyzed three-component coupling of aryl iodides,alkynes and alkenes

A three-component coupling of aryl iodides, alkynes, and alkenes to generate 1,3-butadiene derivatives using layered double hydroxides supported nanopalladium (LDH-Pd⁰) catalyst is described. LDH-Pd⁰ was recovered quantitatively by simple filtration and reused several times with almost consistent activity.     

Efficient Synthesis of 2‐Fluoromethylated Quinolines via Copper‐Catalyzed Alkynylation and Cyclization of Fluorinated Imidoyl Iodides

2‐Fluoromethylated quinolines were synthesized through the reaction of N‐aryl‐fluorinated imidoyl iodides with terminal alkynes in good yields by the catalysis of copper(I) iodide (CuI) alone.     

Palladium Nanoparticles Immobilized on Nano‐Silica Triazine Dendritic Polymer (Pdnp‐nSTDP): An Efficient and Reusable Catalyst for Suzuki–Miyaura Cross‐Coupling and Heck Reactions

A new catalyst based on palladium nanoparticles immobilized on nano‐silica triazine dendritic polymer (Pd_np‐nSTDP) was synthesized and characterized by FT‐IR spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy dispersive X‐ray, transmission electron microscopy and elemental analysis. The size of the palladium nanoparticles was determined to be 3.1±0.5 nm. This catalytic system showed high activity in the Suzuki–Miyaura cross‐coupling of aryl iodides, bromides and chlorides with arylboronic acids and also in the Heck reaction of these aryl halides with styrenes. These reactions were best performed in a dimethylformamide (DMF)/water mixture (1:3) in the presence of only 0.006 mol% and 0.01 mol% of the catalyst, respectively, under conventional conditions and microwave irradiation to afford the desired coupling products in high yields. The Pd_np‐nSTDP was also used as an efficient catalyst for the preparation of a series of star‐ and banana‐shaped compounds with a benzene, pyridine, pyrimidine or 1,3,5‐triazine unit as the central core. Moreover, the catalyst could be recovered easily and reused several times without any considerable loss of its catalytic activity.