芳基碘鎓盐促进芳基化反应的应用

二芳基碘鎓盐属于有机高价碘化合物,具有无毒、反应条件温和以及良好的选择性等优点,在有机合成中具有重要地位,受到广大化学工作者的关注。近年来,利用二芳基碘鎓盐在金属催化下进行的芳基化反应为一些难以合成的杂环化合物的合成提供了简便、高效的方法;同时,二芳基碘鎓盐在无催化剂下进行的芳基化反应,为C—C偶联反应开辟了新的绿色合成路线。本文综述了近年来二芳基碘鎓盐在有机合成中促进芳基化反应的最新进展,着重介绍了利用二芳基碘鎓盐作为芳基化试剂与有机金属试剂、烯烃和炔烃类以及杂环化合物进行芳基化反应的研究;总结了二芳基碘鎓盐与杂环化合物反应中钯催化和铜催化下芳基化反应的机理,最后对二芳基碘鎓盐在今后有机合成中的应用作出了展望。     

有机合成中有机高价碘化合物的研究进展

对高价碘化合物用于有机合成反应，如氧化，加成，取代和交叉偶联的最新进展进行了评述，参考文献82篇。     

有机三价碘试剂在杂环化合物合成中的应用进展

高价碘化学在过去的30年间经历了突飞猛进的发展.作为一类温和、高效、环境友好的非金属氧化试剂,高价碘化合物尤其是有机三价碘试剂被广泛应用于各种杂环化合物骨架的构建中.综述了有机三价碘试剂介导下不同环系杂环化合物合成的新策略及新方法.     

2-碘酰基苯甲酸在有机合成中的研究与应用

高价有机碘化合物的反应性质与过渡金属相似,其参与的反应具有反应条件较温和、选择性好、产率高及环境友好等优点,因而近年来关于高价有机碘试剂的研究受到广泛关注,在有机合成领域中获得了较多应用.综述了近年来高价有机碘试剂2-碘酰基苯基酸(IBX)在有机合成中的研究及应用,包括IBX在氧化羟基、含氮化合物和含硫化合物,在制备αβ-不饱和羰基化合物和α,β-不饱和酯,以及在不对称合成等方面的应用.最后介绍了近期对IBX的改进.     

镍N-杂环卡宾配合物在均相催化偶联反应中的应用

 近十几年来, N-杂环卡宾的配位化学和金属有机化学发展迅速, 已成为均相催化反应中研究最为广泛的配体之一. 在许多过渡金属催化的有机合成反应中特别是偶联反应中, N-杂环卡宾与传统有机膦配体相比具有较高的反应性. 镍价格低廉, 在很多反应中有望替代贵金属钯催化剂. 本文总结了镍 N-杂环卡宾化合物在催化交叉偶联反应和还原偶联反应中的最新应用进展.     

有机锑化合物在交叉偶联反应中的应用研究进展

近年来,有机锑化合物在交叉偶联反应中的应用引起了人们的广泛关注。本文主要对有机锑化合物在交叉偶联反应中的应用作了综述,重点介绍了其在Suzuki交叉偶联反应、Heck偶联反应以及Sonogashira偶联反应中的应用,并展望了其未来的发展方向。     

烷基铝试剂与亲电试剂的偶联反应研究进展

烷基铝试剂因其反应活性高、毒性低、易于制备,广泛应用于有机反应中.过渡金属催化或无催化剂的条件下,有机铝试剂与亲电试剂的交叉偶联反应为多种化合物的合成提供了一种简便的方法,并显示出比有机锂和有机镁试剂更高的官能团耐受性,可以在硝基、酯基、羟基、氨基、腈基和内酯的存在下与羰基进行加成反应,与亲电试剂进行偶联反应.近年来许多有机铝试剂在交叉偶联反应中得到了较广泛的应用.综述了近年来烷基铝试剂在交叉偶联反应中的研究成果,涉及到各种反应体系.     

系列烯基化芳香杂环化合物的合成及结构表征

报道了一个简单、 高选择性合成烯基化芳香杂环化合物的反应体系. 在钯的催化作用下, 以乙酸/乙酸酐或四氢呋喃为溶剂, 芳香杂环化合物与烯基化试剂进行交叉脱氢偶联, 合成了系列具有潜在光学活性的烯基化芳香杂环化合物, 确定了最佳反应条件. 采用紫外光谱、 核磁共振氢谱和X射线单晶衍射对目标化合物进行了表征, 并对反应机理进行了探讨.     

铜催化苯并噻唑与二芳基碘鎓盐的芳基化反应（英文）

二芳基碘盐具有毒性低、反应条件温和及选择性高的优点,在有机合成中一直受到关注,已被广泛用作芳基化试剂,可用于芳杂环化合物的交叉偶联反应和芳基化反应等.发展了一种铜催化下苯并噻唑与二芳基碘鎓盐反应合成2-芳基苯并噻唑衍生物的方法.该方法具有底物范围广泛、基团耐受性良好及产率高等优点.     

可见光光催化:缺电子杂环、苯环与芳基偶氮盐的直接芳基化偶联反应（英文）

发展了可见光照射下Ru(bpy)3(PF6)2催化缺电子杂环C—H活化与芳基偶氮盐的交叉偶联反应.在室温、可见光照射下,各种缺电子杂环与芳基偶氮盐发生高效的偶联反应,同时在相似的条件下,普通苯环也能有效地与芳基偶氮盐偶联形成新C—C键化合物.     

Microwave Assisted Cross-Coupling Reaction of Sodium Tetraphenylborate with Aroyl Chlorides on Palladium-Doped KF/Al2O

The palladium-catalyzed cross-coupling reaction of organoborate compounds with organic electrophiles is very attractive method for organic synthesis. These coupling reactions offer a powerful tool for the formation of carbon-carbon bonds. 1 In the past few years a number of methods have been devoloped which permit the use of organoboron compounds that are thermally stable and inert to water and oxygen. Further these coupling reactions have been used successfully for the synthesis of natural products, pharmaceutical intermediates, and combinatiorial libraries of organic compounds. Sodium tetraphenylborate is a stable, non-toxic and has been used as a phenylating agent affording σ-phenyl complexes of various transition metals by the transfer of a phenyl group from boron to metals. Phenyl transfer from this reagent to some organopalladium complexes making a new carbon-carbon bond has also been noted. Uemura and Huang reported respectively that Pd(0) or Si-P-Pd(0)-catalyzed reaction of acyl chlorides and NaBPh4 proceeded in THF to give the corresponding phenyl ketones. However, only one phenyl group out of four in the borate was available for transfer. Recently, Bumagin reported that the cross-coupling reaction of NaBPh4 with acyl chlorides in the presence of Pd(OAc)2 and Na2CO3 in dry or aqueous acetone to give high yields of unsymmetric ketones. However, the reaction time is long(1-6 h).     

Synthesis of 3-aryl-4-chalcogen-2H-benzopyrans from 3-iodo-4-chalcogen-2H-benzopyrans using a Suzuki cross-coupling

The Suzuki cross-coupling reaction of 3-iodo-4-chalcogen-2H-benzopyran derivatives with a variety of organoboron compounds in the presence of catalytic amount of palladium salt is described. This cross-coupling reaction proceeded cleanly and was performed with aryl boronic acids bearing electron-withdrawing, electron-donating, and neutral substituents, furnishing the corresponding products in moderate to good yields.     

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.     

The palladium-catalyzed “head-to-tail” cross-coupling reaction of 1-alkenylboranes with phenyl or 1-alkenyl iodides. A novel synthesis of 2-phenyl-1-alkenes or 2-alkyl-1,3-alkadienes via organoboranes

The reaction of phenyl or 1-alkenyl iodides with 1-alkenyl-1,3,2-benzodioxaboroles readily obtainable via the hydroboration of 1-alkynes, gives the corresponding “head-to-tail” cross-coupling products, 2-phenyl-1-alkenes or 2-alkyl-1,3-alkadienes, in good yields. The reaction is effectively catalyzed by catalytic amounts of palladium compounds in the presence of triethylamine.     

Reactions of organic halides with organometallic compounds and terminal acetylenes catalyzed by palladium complexes

The results of the investigation of the cross-coupling of organometallic compounds and terminal acetylenes with organic halides catalyzed by transition metal complexes are generalized and analyzed. The influence of different factors on the rate and selectivity of catalytic cross-coupling is discussed. A detailed mechanism of the cross-coupling of Grignard reagents with organic halides is suggested. The cross-coupling reaction involving organotin compounds proceeds under very mild conditions in the presence of a ligand-free Pd catalyst. Examples of using catalytic cross-coupling of organic halides with organomagnesium, organozinc, and organotin compounds are presented.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2148–2167, September, 1996.     

Novel cross-coupling reactions between organotellurides and Grignard reagents employing a MnCl2/CuI catalytic system

We present a general protocol for the cross-coupling reaction of Grignard reagents and organic tellurides. Aryl Grignard reagents react stereospecifically with vinyl tellurides in the presence of a catalytic amount of manganese (II) chloride and copper (I) iodide to produce good yields of the corresponding cross-coupling products.     

Atom-efficient metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles.

The novel metal-catalyzed cross-coupling reaction of indium organometallics with organic electrophiles is described. Triorganoindium compounds (R(3)In) containing alkyl, vinyl, aryl, and alkynyl groups are efficiently prepared from the corresponding lithium or magnesium organometallics by reaction with indium trichloride. The cross-coupling reaction of R(3)In with aryl halides and pseudohalides (iodide 2, bromide 5, and triflate 4), vinyl triflates, benzyl bromides, and acid chlorides proceeds under palladium catalysis in excellent yields and with high chemoselectivity. Indium organometallics also react with aryl chlorides as under nickel catalysis. In the cross-coupling reaction the triorganoindium compounds transfer, in a clear example of atom economy, all three of the organic groups attached to the metal, as shown by the necessity of using only 34 mol % of indium. The feasibility of using R(3)In in reactions with different electrophiles, along with the high yields and chemoselectivities obtained, reveals indium organometallics to be useful alternatives to other organometallics in cross-coupling reactions.     

Dichloroimidazolidinedione-activated one-pot Suzuki–Miyaura cross-coupling of phenols

The first general method for the Suzuki-type cross-coupling of phenols with aryl boronic acids using dichloroimidazolidinedione (DCID) as a new reagent is presented. In the presence of DCID and Pd/metal–organic framework (MOF), coupling of aryl boronic acids with a wide range of phenols, was carried out smoothly in tetrahydrofuran (THF) at reflux conditions to afford the cross-coupling products in good to excellent yields. The structures of all compounds were corroborated by ¹H- and ¹³C-NMR. A plausible mechanism for this type of reaction is proposed.     

Reactions of ethyl bromodifluoroacetate in the presence of copper powder

We have examined the reaction of ethyl bromodifluoroacetate (1) in the presence of copper powder as a procedure for the synthesis of compounds containing a CF₂ group. The complex formed in the above reaction reacted with vinyl or aryl iodides to give cross-coupling products, with Michael acceptors to give 1,4-addition products and with olefins to give radical addition products. The cross-coupling reaction was applied to the synthesis of 4,4-difluoro-α-tocopherol.     

A carrier-free and recyclable protocol for the cross-coupling of terminal alkynes with arylboronic acids in H2O/TBAB

A new and recyclable protocol was developed for Pd(OAc)₂-catalyzed the cross-coupling reaction of terminal alkynes with arylboronic acids using environmentally friendly H₂O/TBAB as reaction medium. A series of cross-coupling products containing internal acetylenic bond can be obtained with good selectivity and yield. The Pd(OAc)₂/H₂O/TBAB system was stable in the Sonogashira-type cross-coupling reaction and could be used at least three cycles without considerable decrease in catalytic performance. The results suggest that the unsupported and recyclable systems can be extended to the other realm of CC bond formation in synthetic organic chemistry.