1,2-二（二苯基膦）乙烷氯化钯(II)的合成及催化活性

以卤化钯（X=Cl、 Br、 I）为原料,乙腈为溶剂,与1,2-二（二苯基膦）乙烷反应,合成了1,2-二（二苯基膦）乙烷卤化钯[Pd(dppe)X₂, dppe=1,2-二（二苯基膦）乙烷],产率均高于96％,其结构经¹H NMR, XRD和元素分析确证。以Suzuki反应和Stille C—C偶联反应为模板反应,研究了Pd(dppe)Cl₂的催化活性。结果表明：Pd(dppe)Cl₂对2-氯噻吩和对甲氧基苯硼酸的Suzuki偶联反应、4,7-二氯苯并噻二唑核或其他含苯并噻二唑核的卤代芳烃与其他芳香核的锡试剂的Stille C—C偶联反应的催化转化率分别为80%~85%和52%~60%,催化活性优于四（三苯基膦）钯(70%~85%和43%~50%)。     

卤素取代甲苯的合成及其在Co(OAc)2－Mn(OAc)2－NaBr催化下的液相氧化反应

合成了3-氟甲苯和另外5个氯或溴取代的3-氟甲苯,以Co(OAc)₂·4H₂O、Mn(OAc)₂·4H₂O和NaBr为催化剂用液相氧化反应将其氧化为相应的卤代苯甲酸。该反应产率较高,所得卤代苯甲酸纯度好。6个卤代的3-氟甲苯及6个相应的卤代苯甲酸其结构经IR、UV、¹H NMR、MS和元素分析所确证。     

卤代化合物的光化学反应研究进展

介绍近年来卤代化合物在光照射下的偶联反应、醇解反应、消去反应、开环反 应，尤其是卤代杂环化合物的光化学反应，得到了许多用热反应或催化反应无法替 代的具有生物(理)活性的中间体．     

离子液体中卤代炔烃高效水解制取α-卤代甲基酮的研究

在离子液体中,硫酸促进卤代炔烃水解生成α-卤代甲基酮,反应收率高达85%~94%.离子液体-硫酸反应体系可多次(5次以上)循环使用而不影响反应收率.同时,此反应体系底物适用性强,高效制得一系列芳环上不同取代基的(如甲基、甲氧基、羟基、硝基等)α-氯/溴/碘代苯乙酮及脂肪类卤代甲基酮.     

微乳介质中卤代芳烃Ullmann偶联反应

微乳介质中卤代芳烃Ullmann偶联反应;偶联反应;微乳;卤代芳烃     

一种简单、 高效合成α-卤代甲基酮化合物的新方法

发展了一种简单、 高效、 温和的卤代炔烃水合反应体系. 在阳离子金催化剂的催化作用下, 以二氯乙烷为溶剂, 室温下卤代炔烃发生水合反应, 高收率、 高区域选择性地得到单一的α-卤代甲基酮化合物(收率≥91%). 该方法具有底物适用范围广、 反应条件温和和环境友好等优点, 为含α-卤代甲基酮结构单元的天然产物及复杂药物分子的合成提供了新方法.     

饮用水消毒副产物测定方法的研究进展

饮用水消毒副产物(DBPs)是指在对饮用水消毒的过程中,水中的各类有机物与消毒剂发生反应生成的化合物。对三卤甲烷、卤代乙酸、卤代乙腈、亚硝胺、卤代对苯醌、卤酸盐(氯酸盐、次氯酸盐和溴酸盐等)6类DBPs的前处理技术与检测方法进行综述,介绍了DBPs研究领域取得的进展,并对今后的研究方向进行了展望。     

二碘化钐在脱氧、还原和碳-碳键形成反应中的应用

本文研究了二碘化钐对一些有机化合物的脱氧反应, 以及它在醇存在下对α-卤代酮、偶氮苯和苯醌的还原反应。首次报道了在二碘化钐作用下α-卤代酮与醛之间的碳-碳键形成瓜在, 高产率地制备了各种α,β-不饱和酮; 同时提出了涉及由α-卤代酮同时与Sm(II)和Sm(III)/I^-物种作用形成烯醇钐盐中间体的可能机理。     

3-(2喹啉基) 酚酮的卤代和硝化反应

本文首次报道了3-(2喹啉基) 酚酮的卤代和硝化反应在冰乙酸介质中,3-(2喹啉基) 酚酮与溴反应,在不同条件下分别得到单溴代产物和双溴代产物; 与硝酸反应得到单硝酸化产物,与过量硝酸反应,得到的硝化产物。     

卤代荧光素与西布曲明的荧光猝灭和褪色光谱及其分析应用

在弱酸性缓冲溶液中,乙基曙红(EE)、赤藓红(ET)和荧光桃红(PX)3种卤代荧光素与盐酸西布曲明(SH)形成离子缔合物,导致吸收光谱发生变化和荧光猝灭。研究了反应产物的吸收和荧光光谱特征,适宜的反应条件,据此建立了以卤代荧光素为光谱探针的灵敏、简便、快速测定SH的新方法。其中ET体系褪色反应灵敏度最高,对SH的线性范围为0.1～4.0μg/mL,检出限为0.06μg/mL;PX-SH体系的荧光猝灭法对SH的线性范围是0.2～4.6μg/mL(λex/λem=540nm/560nm),检出限为0.09μg/mL。讨论了离子缔合反应对荧光及吸收光谱的影响及卤代荧光素荧光猝灭和褪色的原因。     

Palladium-catalyzed cross-coupling reactions of coumarin derivatives: An overview

Coumarins are omnipresent in several plants and exhibit a plethora of pharmacological properties, making them an important scaffold in organic synthesis. Naturally, the chemistry of this motif has attracted ever-increasing attention, among which palladium-catalyzed coupling reactions are the most prevalent one. Numerous useful, easy, and concise syntheses and reactions have been achieved using palladium-catalyzed coupling reactions. This review focuses on recent advances in palladium-catalyzed cross-coupling reactions such as Suzuki, Heck, Stille, Sonogoshira etc. reactions of coumarin derivatives and covers the literature from 2001 to 2020.     

Pyrrolodiazines. 6. Palladium-catalyzed arylation, heteroarylation, and amination of 3,4-dihydropyrrolo[1,2-a]pyrazines

The palladium-catalyzed Suzuki cross-coupling reaction of arylboronic acids and 6-bromo- and 6,8-dibromo-3,4-dihydropyrrolo[1,2-a]pyrazines afforded 6-substituted and 6,8-disubstituted 3,4-dihydropyrrolo[1,2-a]pyrazines in good yields. Stille and Negishi coupling reactions have been used to prepare 6-heteroaryl-substituted derivatives in moderate yields by employing heteroaryl halides and 6-metalated 3,4-dihydropyrrolo[1,2-a]pyrazines as reaction partners. A variety of cyclic secondary amines have also been incorporated at position C-6 of 6-bromo-1-phenyl-3,4-dihydropyrrolo[1,2-a]pyrazine in the presence of the palladium catalyst Pd(2)(dba)(3) in conjunction with BINAP as ligand. This amination reaction is one of the few reported examples of such a palladium-catalyzed transformation on a pyrrole ring, although the reaction could not be extended to less nucleophilic amines.     

Evaluation of polymer-supported vinyltin reagents in the Stille cross-coupling reaction

The synthesis of two new vinyltin reagents grafted on an insoluble macroporous polymer is reported. These reagents were used in the palladium-catalyzed Stille cross-coupling reaction with aryl halides. In all reactions, the conversion of the starting aryl halide is high and the amount of organotin by-product is particularly low (at the end of the catalytic run, the amount of Sn is up to 16 ppm in the crude reaction mixture removed of the insoluble polymer, and it is less than 1 ppm in the product purified by chromatography on silica gel).     

An efficient Stille cross-coupling reaction catalyzed by Pd(OAc)2/DAB-Cy catalytic system

An efficient palladium-catalyzed Stille cross-coupling reaction has been developed. In the presence of 3 mol% of Pd(dba)₂ and 6 mol% of DAB-Cy (1,4-dicyclohexyl-diazabutadiene), various aryl halides (iodides and bromides) were coupled with organotin compounds to afford the corresponding biaryls and alkyne in good to excellent yields. Furthermore, high TONs [turnover numbers, TONs up to 950,000 for the reaction of 1-iodo-4-nitrobenzene and tributyl(phenyl)stannane] for the Stille cross-coupling reaction were observed.     

Activation and functionalization of benzylic derivatives by palladium catalysts

Palladium-catalyzed transformations of aryl halides and pseudo-halides involving carbonylation, carbon-carbon and carbon-heteroatom bond-forming reactions, etc. are very well documented, and have already been reviewed several times. The metal-catalyzed activation of benzylic derivatives is much less described. However, during the last decades, a number of papers have shown the interest offered by benzylic derivatives (halides, carbonates, acetates, phosphonates) in selective catalytic reactions for organic synthesis, most of them in the presence of palladium catalysts. The purpose of this tutorial review is to highlight selected examples of palladium-catalyzed transformations involving reactive benzylic derivatives.     

钯催化卤代芳烃Ullmann偶合反应

Ullmann偶合反应是有机合成中构建碳—碳键最重要的方法之一. 综述了钯催化卤代芳烃Ullmann偶合反应的研究进展, 其中包括钯催化还原Ullmann偶合反应和钯催化氧化Ullmann偶合反应等两部分.     

The cross-coupling reactions of organic halides with organic derivatives of tin,mercury and copper catalyzed by palladium

The palladium-catalyzed cross-coupling of organic halides with organometallic compounds of tin, mercury and copper is discussed. It is shownn that the “ligandless” palladium complexes RPdXL₂ (L = solvent), in which solvent molecules act as weak donating ligands, are the most active catalysts for reactions of organotin compounds. It is found that nucleophilic catalysis is an efficient method of activatioin of organomercury and organocopper compounds in cross-coupling reactions. In the presence of iodide ion the palladium-catalyzed reactions of these compounds proceed under mild conditions giving high yields of cross-coupling products.     

Palladium-catalyzed syntheses of tetrahydrocarbazolones as advanced intermediates to carbazole alkaloids

Two sequential palladium-catalyzed reactions, an intermolecular Stille cross-coupling followed by a recently developed palladium-catalyzed reductive N-heteroannulation, have been employed as the key synthetic steps toward six tetrahydrocarbazolones. The products are advanced intermediates toward a number of naturally occurring carbazole alkaloids.     

Palladium-catalyzed cross-coupling reactions of aryl mesylates

Palladium-catalyzed cross-coupling reactions are state-of-the art methods for synthesis of many important compounds. The development of the use of the phenol-derived sulfonated hydroxyl group in the coupling reactions is highly attractive as the hydroxyl group is commonly present in organic compounds and they are versatile alternatives to aryl halides in cross-coupling reactions. In this tutorial review, we summarize the current development of palladium-catalyzed cross-coupling reactions of aryl mesylates.     

胺作为配体在钯催化偶联反应中应用

对近期我们研究小组及其它研究小组在利用胺作为钯催化偶联反应的配体研究进展进行了总结. 钯/胺作为催化体系主要应用的偶联反应包括: Suzuki-Miyaura交叉反应, Sonogashira交叉反应, Stille交叉反应, Hiyama交叉反应和Heck反应. 研究结果表明胺可以作为价廉和高效的配体促进钯催化交叉偶联反应.