共查询到19条相似文献,搜索用时 984 毫秒
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合成并表征了一类含新型胺基膦配体的Grubbs二代型钌卡宾烯烃复分解催化剂[RuCl2(H2IMes)·(R1HNPR22)(=CHPh)], 采用核磁共振波谱和单晶X射线衍射确定了催化剂的结构. 在室温条件下, 以N,N-二烯丙基-对甲苯磺酰胺的关环复分解反应(RCM)为模型, 考察了不同胺基膦配体对钌卡宾催化反应速率的影响. 结果表明, G2?1表现出最佳的催化活性. 通过底物研究发现, G2?1催化剂(摩尔分数, 1%)对双端烯及多端烯的RCM反应具有较好的活性和官能团适应性, 产物收率均>95%; G2?1催化剂同样适用于同(异)端烯底物的交叉复分解反应(CM), 其催化苯乙烯与3-苯氧基丙烯的CM反应时产物收率高达92%. 相似文献
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为了得到稳定性更好、活性更高的烯烃复分解催化剂,本文采用有机合成的方法,以钌卡宾烯烃复分解催化剂为主体,用锌卟啉进行修饰,得到锌卟啉修饰的Grubbs-Hoveyda型双核钌卡宾烯烃复分解反应催化剂,产物结构使用核磁共振方法进行表征。 用0.1%化学计量催化剂催化几种代表性底物闭环复分解(RCM)反应产率能达到95%,对于特定的交叉烯烃复分解反应(CM),延长反应时间也能得到93%的较高产率。 研究结果为Grubbs-Hoveyda催化剂的修饰提供了新方法和理论依据。 相似文献
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核苷类似物可以参与并干扰细菌(病毒)的DNA或RNA过程,抑制其生长和繁殖,从而有希望发展为抗肿瘤抗病毒药物。一些天然的核苷化合物虽然表现出一定的生理活性,在体内缺乏酶稳定性和靶向选择性却限制了其在医药领域的应用,合成具有生物活性的化学修饰的核苷及其衍生物是核酸药物化学中的重要课题。一类在金属卡宾复合物催化下的分子内或分子间烯烃重组反应-----复分解反应的发展使核苷类似物的合成进入了新阶段, 烯烃复分解反应成为核苷类似物合成的主要途径之一。随着施洛克催化剂、格拉布催化剂等复分解反应催化剂的发现和不断改进,烯烃复分解反应,尤其是关环复分解和交叉复分解反应被广泛应用于构建核苷类似物的糖环(或伪糖)结构或连接核苷类似物单体而形成核苷多聚物。本文对烯烃复分解反应在核苷类似物包括碳环核苷,2’,3’-双脱氧核苷,无环核苷,多环核苷及核苷二聚体或三聚体的合成中的应用进行了综述。 相似文献
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结合本研究小组的相关课题工作,综述了苯乙烯内酯类天然产物全合成方法的 研究进展。主要包括以呋喃甲醇类化合物的氧化重排反应、烯烃复分解环化反应( RCM)和酸催化的酯化关环等作为关键反应的方法。 相似文献
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铁氧化物催化类Fenton反应 总被引:3,自引:0,他引:3
高级氧化技术是当今水处理技术领域研究的热点,Fenton试剂因操作简单、反应条件温和及氧化效率高等优势而备受关注。铁氧化物催化类Fenton反应能有效地解决催化剂回收利用难等问题,并且能够在较为广泛的pH范围内使用,从而成为Fenton氧化领域一个新的研究方向,但反应过程和机制往往更为复杂。本文评述了铁氧化物催化类Fenton反应中可能存在的多种机理,主要是羟基自由基理论、氧空位机理和高价态铁络合物机制。类Fenton反应速率的限速步骤是Fe(Ⅲ)/Fe(Ⅱ)循环过程,从提高反应速率的机理出发,本文探讨了类Fenton反应中铁氧化物催化剂的制备和发展,催化剂中多种价态的铁元素,通过相互间发生电子转移以加速Fe(Ⅱ)的再生,提高反应效率。铁氧化物掺杂过渡金属能显著提高催化H2O2有效分解的活性。阐明了多金属掺杂铁氧化物中多金属组分的催化机制和铁氧化物结构形态对反应性能的影响。研究表明催化剂中铁的结构形态、催化剂比表面积、催化剂与H2O2之间电子转移速率等都是决定催化剂性能的重要因素。最后讨论了继续研究方向,为开展非均相类Fenton反应提供参考。 相似文献
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The use of metathesis, especially in the context of ring-closing metathesis (RCM) to form five- and six-membered rings, is widespread in organic chemistry today. However, there are surprisingly few examples of the reaction being used to form aromatic compounds. The central place of aromatic compounds in both medicinal chemistry and natural products synthesis, coupled with the efficiency and functional group tolerance of RCM catalysts, means that there is now an interesting opportunity to use RCM for the synthesis of arenes. Although the formation of an aromatic compound was viewed in many early examples as an undesirable degradation product, several rationally designed methods towards the preparation of aromatic compounds by RCM have recently been developed. 相似文献
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Matsuya Y Takayanagi S Nemoto H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(17):5275-5281
For the synthesis of a 12-membered salicylic macrolide scaffold, ring-closing metathesis (RCM) of a omega-diene compound was planned. The stereochemical outcome of the RCM reaction changed depending on the type of Ru catalyst that was used; a "first-generation" Grubbs catalyst produced exclusively the E isomer and "second-generation" catalysts provided a mixture of the E and Z isomers under kinetic control (not thermodynamic control). Considerations for the E/Z selectivity are described. 相似文献
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Noy B. Nechmad Ravindra Phatake Elisa Ivry Albert Poater N. Gabriel Lemcoff 《Angewandte Chemie (International ed. in English)》2020,59(9):3539-3543
The development of selective olefin metathesis catalysts is crucial to achieving new synthetic pathways. Herein, we show that cis‐diiodo/sulfur‐chelated ruthenium benzylidenes do not react with strained cycloalkenes and internal olefins, but can effectively catalyze metathesis reactions of terminal dienes. Surprisingly, internal olefins may partake in olefin metathesis reactions once the ruthenium methylidene intermediate has been generated. This unexpected behavior allows the facile formation of strained cis‐cyclooctene by the RCM reaction of 1,9‐undecadiene. Moreover, cis‐1,4‐polybutadiene may be transformed into small cyclic molecules, including its smallest precursor, 1,5‐cyclooctadiene, by the use of this novel sequence. Norbornenes, including the reactive dicyclopentadiene (DCPD), remain unscathed even in the presence of terminal olefin substrates as they are too bulky to approach the diiodo ruthenium methylidene. The experimental results are accompanied by thorough DFT calculations. 相似文献
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Chelating Ruthenium Phenolate Complexes: Synthesis,General Catalytic Activity,and Applications in Olefin Metathesis Polymerization 下载免费PDF全文
Anna Kozłowska Dr. Maciej Dranka Prof. Janusz Zachara Eva Pump Prof. Dr. Christian Slugovc Krzysztof Skowerski Prof. Dr. Karol Grela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):14120-14125
Cyclic Ru‐phenolates were synthesized, and these compounds were used as olefin metathesis catalysts. Investigation of their catalytic activity pointed out that, after activation with chemical agents, these catalysts promote ring‐closing metathesis (RCM), enyne and cross‐metathesis (CM) reactions, including butenolysis, with good results. Importantly, these latent catalysts are soluble in neat dicyclopentadiene (DCPD) and show good applicability in ring‐opening metathesis polymeriyation (ROMP) of this monomer. 相似文献
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Daniel Rost 《Tetrahedron letters》2008,49(41):5968-5971
Highly efficient formation of tetrasubstituted olefins is described by ring-closing metathesis (RCM) using catalyst 2 in presence of hexafluorobenzene. This combination with hexafluorobenzene shows an unexpected promoting effect, which requires low catalysts loadings and allows the conversion of deficient olefins in high yields and very short reaction times. 相似文献
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Costabile C Mariconda A Cavallo L Longo P Bertolasi V Ragone F Grisi F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(31):8618-8629
The synthesis of Ru-based precatalysts with N-heterocyclic carbene (NHC) ligands bearing syn- and anti-methyl groups on the NHC backbone and aryl N-substituents with differing steric bulk was carried out. The catalytic behavior of the monophospine Ru precatalysts (7a, 7b, 8a, and 8b) was compared to the corresponding family of phosphine-free catalysts (9a, 9b, 10a and 10b) in the ring-closing metathesis (RCM) of olefins. These catalysts showed high efficiency in RCM reactions and the syn-isomers 7a and 9a, in particular, proved to be among the most active catalysts in the formation of tetrasubstituted olefins through RCM. DFT studies on the entire RCM catalytic cycle of hindered olefins were performed to rationalize the different behaviors of catalysts with syn- and anti-methyl groups on the NHC backbone. Theoretical results not only disclosed how NHC symmetry influences the overall activity of the catalyst, but also gave relevant and more general indications on the crucial steps of the RCM of olefins. 相似文献
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Hervé Clavier 《Journal of organometallic chemistry》2005,690(15):3585-3599
New recyclable imidazolium-tagged ruthenium catalysts have been developed to perform olefin metathesis in room temperature ionic liquids (RTILs). High level of recyclability combined with a high reactivity were obtained in the ring-closing metathesis (RCM) of a variety of di- or tri-substituted and/or oxygen-containing dienes. Extremely low residual ruthenium levels were detected in the RCM products (average of 7.3 ppm per run). Several examples of olefin cross-metathesis (CM) have been also studied. 相似文献
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Naoual Bakhrou 《Tetrahedron letters》2010,51(30):3935-5536
Glycerol, a biodegradable and virtually non-toxic bio-sourced chemical can be used as an alternative, reusable, sustainable solvent, with so far limited application in the field of green organic chemistry. Herein, the reaction conditions have been screened for the ring-closing metathesis (RCM) of N,N-diallyltosylamine and diethyl diallylmalonate in glycerol, under microwave irradiation and in the presence of the most common commercially available RCM catalysts. The products were isolated in high yield after extraction and the catalyst could be recycled up to two times. Results with simultaneous cooling of the reaction vessel under microwave irradiation are also reported. 相似文献
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Krause JO Nuyken O Wurst K Buchmeiser MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):777-784
The synthesis and heterogenization of new Grubbs-Hoveyda type metathesis catalysts by chlorine exchange is described. Substitution of one or two chlorine ligands with trifluoroacetate and trifluoromethanesulfonate was accomplished by reaction of [RuCl(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (IMesH(2) = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) with the silver salts CF(3)COOAg and CF(3)SO(3)Ag, respectively. The resulting compounds, [Ru(CF(3)SO(3))(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (1), [RuCl(CF(3)SO(3))([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (2), and [Ru(CF(3)CO(2))(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (3) were found to be highly active catalysts for ring-closing metathesis (RCM) at elevated temperature (45 degrees C), exceeding known ruthenium-based catalysts in catalytic activity. Turn-over numbers (TONs) up to 1800 were achieved in RCM. Excellent yields were also achieved in enyne metathesis and ring-opening cross metathesis using norborn-5-ene and 7-oxanorborn-5-ene-derivatives. Even more important, 3 was found to be highly active in RCM at room temperature (20 degrees C), allowing TONs up to 1400. Heterogeneous catalysts were synthesized by immobilizing [RuCl(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] on a perfluoroglutaric acid derivatized polystyrene-divinylbenzene (PS-DVB) support (silver form). The resulting supported catalyst [RuCl(polymer-CH(2)-O- CO-CF(2)-CF(2)-CF(2)-COO)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (5) showed significantly reduced activities in RCM (TONs = 380) compared with the heterogeneous analogue of 3. The immobilized catalyst, [Ru(polymer-CH(2)-O-CO-CF(2)-CF(2)-CF(2)-COO)(CF(3)CO(2))([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (4) was obtained by substitution of both Cl ligands of the parent Grubbs-Hoveyda catalyst by addition of CF(3)COOAg to 5. Compound 4 can be prepared in high loadings (160 mg catalyst g(-1) PS-DVB) and possesses excellent activity in RCM with TONs up to 1100 in stirred-batch RCM experiments. Leaching of ruthenium into the reaction mixture was unprecedentedly low, resulting in a ruthenium content <70 ppb (ng g(-1)) in the final RCM-derived products. 相似文献