共查询到19条相似文献,搜索用时 156 毫秒
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钯催化下有机锡化合物的偶联反应在碳-碳键形成过程中的应用 总被引:2,自引:0,他引:2
本文述评了最近几年来钯催化的有机锡化合物与有机亲电试剂的交叉偶联反应在有机合成中用于碳-碳键形成的主要研究成果。主要讨论了直接交叉偶联反应,CO或烯键插入的交叉偶联反应和机理。 相似文献
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有机硫化合物广泛应用于医药、农药、新材料等领域, 因此, 发展新的碳-硫键形成方法非常重要. 近年来, 烯烃的自由基砜基化反应作为一种温和、有效的有机硫化合物合成策略得到了快速发展, 其中, 烯烃的硫砜基化反应因为能够同时构建两种不同的碳-硫键成了一种非常有吸引力的碳-硫键形成方法. 以硫代磺酸酯同时作砜基化和硫化试剂, 实现了一个可见光催化烯烃砜基化启动的远程醛基碳-氢键直接硫化反应, 一步合成了6-或7-砜基取代的硫酯类化合物. 反应具有优秀的原子经济性, 产率中等到良好, 能兼容各种不同的官能团. 相比传统的烯烃1,2-或1,1-硫砜基化反应, 首次实现了官能团化烯烃的远程硫砜基化反应, 拓展了现有硫砜基化反应方法学. 初步的机理研究表明, 该反应可能经历一个可见光催化的自由基反应历程. 相似文献
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2005年诺贝尔化学奖授予在烯烃复分解合成转换方面做出重要贡献的3位科学家:Y ves Chauvin,Richard R.Schrock和Robert H.Grubbs.简要介绍了3位获奖者的主要贡献,烯烃复分解反应的分类和催化反应机理,金属卡宾催化剂及烯烃复分解反应的一些应用.另外,介绍了此领域目前研究的主要科学问题. 相似文献
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Dr. Johan Bidange Dr. Cédric Fischmeister Dr. Christian Bruneau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12226-12244
Remarkable innovations have been made in the field of olefin metathesis due to the design and preparation of new catalysts. Ethenolysis, which is cross‐metathesis with ethylene, represents one catalytic transformation that has been used with the purpose of cleaving internal carbon–carbon double bonds. The objectives were either the ring opening of cyclic olefins to produce dienes or the shortening of unsaturated hydrocarbon chains to degrade polymers or generate valuable shorter terminal olefins in a controlled manner. This Review summarizes several aspects of this reaction: the catalysts, their degradation in the presence of ethylene, some parameters driving their productivity, the side reactions, and the applications of ethenolysis in organic synthesis and in potential industrial applications. 相似文献
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Among the many types of transition-metal-catalyzed C-C bond-forming reactions, olefin metathesis has come to the fore in recent years owing to the wide range of transformations that are possible with commercially available and easily handled catalysts. Consequently, olefin metathesis is now widely considered as one of the most powerful synthetic tools in organic chemistry. Until recently the intermolecular variant of this reaction, cross-metathesis, had been neglected despite its potential. With the evolution of new catalysts, the selectivity, efficiency, and functional-group compatibility of this reaction have improved to a level that was unimaginable just a few years ago. These advances, together with a better understanding of the mechanism and catalyst-substrate interactions, have brought us to a stage where more and more researchers are employing cross-metathesis reactions in multistep procedures and in the synthesis of natural products. The recent inclusion of alkynes and hindered bicyclic olefins as viable substrates for bimolecular metathesis coupling, the discovery of enantioselective cross-metathesis and cross-metathesis in water, and the successful marriage of metathesis and solid-phase organic synthesis has further widened the scope of this versatile reaction. 相似文献
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Grzegorz K. Zieliński Prof. Dr. Karol Grela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9440-9454
Since olefin metathesis transformation has become a favored synthetic tool in organic synthesis, more and more distinct non‐metathetical reactions of alkylidene ruthenium complexes have been developed. Depending on the conditions applied, the same olefin metathesis catalysts can efficiently promote isomerization reactions, hydrogenation of C=C double bonds, oxidation reactions, and many others. Importantly, these transformations can be carried out in tandem with olefin metathesis reactions. Through addition of one portion of a catalyst, a tandem process provides structurally advanced products from relatively simple substrates without the need for isolation of the intermediates. These aspects not only make tandem catalysis very attractive from a practical point of view, but also open new avenues in (retro)synthetic planning. However, in the literature, the term “tandem process” is sometimes used improperly to describe other types of multi‐reaction sequences. In this Concept, a number of examples of tandem catalysis involving olefin metathesis are discussed with an emphasis on their synthetic value. 相似文献
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Solvents play a critical role in “greening” synthetic chemistry, and this is also true in catalytic organic synthesis. This review attempts to summarize the progress made in the past a few years on homogeneous and heterogeneous catalytic reactions in the non-conventional solvents, water, ionic liquids, supercritical carbon dioxide and fluorous carbons, with the focus on those catalyzed by transition metal complexes. The reactions covered include hydrogenation, hydroformylation, carbonylation, Heck reactions, Suzuki and Stille couplings, Sonogashira reactions, allylic substitution, olefin metathesis, olefin epoxidation and alcohol oxidation. 相似文献
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Matthias Schuster Siegfried Blechert 《Angewandte Chemie (International ed. in English)》1997,36(19):2036-2056
Transition metal catalyzed C? C bond formations belong to the most important reactions in organic synthesis. One particularly interesting reaction is olefin metathesis, a metal-catalyzed exchange of alkylidene moieties between alkenes. Olefin metathesis can induce both cleavage and formation of C? C double bonds. Special functional groups are not necessary. Although this reaction—which can be catalyzed by numerous transition metals—is used in industry, its potential in organic synthesis was not recognized for many years. The recent abrupt end to this Sleeping-Beauty slumber has several reasons. Novel catalysts can effect the conversion of highly fictionalized and sterically demanding olefins under mild reaction conditions and in high yields. Improved understanding of substrate–catalyst interaction has greatly contributed to the recent establishment of olefin metathesis as a synthetic method. In addition to the preparation of polymers with fine-tuned characteristics, the metathesis today also provides new routes to compounds of low molecular weight. The highly developed ring-closing metathesis has been proven to be key step in the synthesis of a growing number of natural products. At the same time interesting applications can be envisioned for newly developed variants of bimolecular metathesis. Improvements in the selective cross-metathesis of acyclic olefins as well as promising attempts to include alkynes as viable substrates provide for a vivid development of the metathesis chemistry. 相似文献
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Synthesis of a C-analogue of bacterial glycolipid BbGL2 is reported using Grignard reaction of in situ generated beta-galactosyl iodide and subsequent olefin cross metathesis reaction of C-vinyl galactoside as key steps. [reaction: see text] 相似文献
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Vougioukalakis GC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(29):8868-8880
Olefin metathesis has revolutionized the way chemists design and synthesize molecules, mostly due to the development of well-defined ruthenium catalysts with high oxygen-, moisture-, and functional-group tolerance. However, the complete removal of residual ruthenium after the end of a metathesis reaction often imposes significant challenges. This Minireview summarizes the strategies for the sequestration of ruthenium impurities from olefin metathesis post-reaction mixtures, thus comprising a practical guide for synthetic chemists employing ruthenium-catalyzed metathesis reactions in the synthesis of organic or polymeric materials. 相似文献