共查询到20条相似文献,搜索用时 15 毫秒
1.
Woodward CP Spiccia ND Jackson WR Robinson AJ 《Chemical communications (Cambridge, England)》2011,47(2):779-781
Acyclic diamines are valuable feedstocks for polyamide synthesis. Ruthenium-alkylidene catalysed cross metathesis of amino alkenes is problematic and acyl derivatisation can result in less efficient syntheses, poor catalyst turnover and isomerisation. Temporary amine masking via stable and soluble ammonium salts delivers cyclic and acyclic aminoalkenes in high yield and purity. 相似文献
2.
《Journal of organometallic chemistry》2006,691(24-25):5289-5297
Synthesis and screening of catalytic activity of novel mono- and diruthenium carbene complexes 7a and 7b prepared from inexpensive Bisphenol S via Claisen rearrangement–isomerisation route is described. These catalysts constitute an excellent tool for ring-closing metathesis by combining high stability with increased catalytic activity as compared with the parent Hoveyda–Grubbs catalyst. 相似文献
3.
Michrowska A Mennecke K Kunz U Kirschning A Grela K 《Journal of the American Chemical Society》2006,128(40):13261-13267
A new concept for noncovalent immobilization of a ruthenium olefin metathesis catalyst is presented. The 2-isopropoxybenzylidene ligand of a Hoveyda-Grubbs carbene is further modified by an additional amino group (7) and immobilization is achieved by treatment with sulfonated polystyrene forming the corresponding ammonium salt. In this novel strategy for the immobilization of ruthenium-based metathesis catalysts, the amino group plays a two-fold role, being first an active anchor for immobilization and second, after protonation, activating the catalysts (electron donating to electron withdrawing activity switch). The polymeric support was prepared by precipitation polymerization which led to small bead sizes (0.2-2 microm) and large surface areas. Compared to commercial resins this tailor-made phase showed superior properties in immobilization of complex 7. This concept of immobilization was applied to glass-polymer composite megaporous Raschig rings. Ru catalyst 7 on Raschig rings was used under batch conditions in various metathesis reactions, including ring-closing (RCM), cross- (CM) and enyne metathesis, to give products of high chemical purity with very low ruthenium contamination levels (21-102 ppm). The same ring can be used for up to 6 cycles of metathesis. 相似文献
4.
A Grubbs-Hoveyda-Type metathesis catalyst bearing a tris(perfluoroalkyl)silyl tag was immobilized in the fluorophilic phase of amphiphilic conetworks (APCNs). This catalytic system was applied to ring-closing metathesis (RCM) reactions in aqueous media. Different substrates were evaluated and with 10 mol% of catalyst at 60 °C good conversions were observed. Reuse of the catalytic system was possible, but resulted generally in lower conversions. 相似文献
5.
Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts. 相似文献
6.
Highly active water-soluble olefin metathesis catalyst 总被引:4,自引:0,他引:4
A novel water-soluble ruthenium olefin metathesis catalyst supported by a poly(ethylene glycol) conjugated saturated 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligand is reported. The catalyst displays improved activity in ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis reactions in aqueous media. 相似文献
7.
A unique example of sequential ring-closing metathesis and cross-enyne metathesis is reported. Here, the in situ generated ethylene by product from ring-closing metathesis is trapped by alkyne moiety. No metathesis product formation was observed with more reactive second generation catalyst in the absence of ethylene. Differential chemoselectivity with the first and second generation Grubbs’ catalyst has been observed when the reaction was performed in presence of the external source of ethylene. 相似文献
8.
Justin P. Gallivan 《Tetrahedron letters》2005,46(15):2577-2580
A water-soluble ruthenium-based olefin metathesis catalyst supported by a poly(ethylene glycol) conjugated N-heterocyclic carbene ligand is reported. The catalyst displays greater activity in aqueous ring-opening metathesis polymerization (ROMP) reactions than previously reported water-soluble metathesis catalysts. 相似文献
9.
Michaël Raymond Michael Holtz‐Mulholland Prof. Shawn K. Collins 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(40):12763-12767
Macrocyclic olefin metathesis has seen advances in the areas of stereochemistry, chemoselectivity, and catalyst stability, but strategies aimed at controlling dilution effects in macrocyclizations are rare. Herein, a protocol to promote macrocyclic olefin metathesis, one of the most common synthetic tools used to prepare macrocycles, at relatively high concentrations (up to 60 mM ) is described by exploitation of a phase‐separation strategy. A variety of macrocyclic skeletons could be prepared having either different alkyl, aryl, or amino acids spacers. 相似文献
10.
Megha Jagadale Sharanabasappa Khanapure Rajashri Salunkhe Mohan Rajmane Gajanan Rashinkar 《应用有机金属化学》2016,30(3):125-131
A silica‐supported ionic liquid phase catalyst containing Keggin‐type anion has been prepared by covalent grafting of ferrocene‐tagged ionic liquid in a matrix of silica followed by anion metathesis reaction. This novel catalyst served as a robust heterogeneous catalyst for the synthesis of biologically active sulfonamides from 4‐toluenesulfonyl chloride and amines. Additionally, recycling experiments showed that the catalyst could be reused five times. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
11.
Aldoximes have been isomerised to corresponding amides, using silica gel as catalyst. This method is found to be much better than other methods for simplicity and high conversions. Unlike acid-catalysed isomerisation, the nitrile is not an intermediate in this isomerisation. 相似文献
12.
P. Meriaudeau R. Bacaud L.Ngoc Hung Anh.T. Vu 《Journal of molecular catalysis. A, Chemical》1996,110(3):L177-L179
The isomerisation of n-butene into isobutene has been studied over a ferrierite catalyst being in a selective state (aged catalyst) or non-selective state (fresh catalyst). It is observed, by using 13C=C---C---C, that a bimolecular process operates on the non-selective catalyst whereas a monomolecular process exists on the selective catalyst. 相似文献
13.
Poulomi Mondal Latibuddin Thander Shital K. Chattopadhyay 《Tetrahedron letters》2012,53(11):1328-1331
A new synthesis of phenanthridine derivatives having three-point diversity has been developed based on the sequential application of three-atom economic processes viz. aza-Claisen rearrangement, ring-closing enyne metathesis and Diels–Alder reaction as key steps. An unexpected isomerisation was observed during aza-Claisen rearrangement of N-allylanilines which may open up new opportunities in heterocyclic synthesis. 相似文献
14.
Highly stereoselective formation of cis-2-ene-1,4-diesters by homo- and heterocoupling of alpha-diazoacetates in the presence of Grubbs second-generation catalyst is demonstrated. The dual reactivity of the catalyst in alkene metathesis and diazocoupling has been exploited in the synthesis of 12-26-membered macrocyclic dienyl dilactones by one-pot carbene dimerisation/ring-closing metathesis. 相似文献
15.
The synthesis of a fluorous olefin metathesis catalyst derived from the Grubbs second-generation ruthenium carbene complex is described. The air stable fluorous polymer-bound ruthenium carbene complex 1 shows high reactivity in effecting the ring-closing metathesis of a broad spectrum of diene and enyne substrates leading to the formation of di-, tri-, and tetrasubstituted cyclic olefins in minimally fluorous solvent systems (PhCF3/CH2Cl2, 1:9-1:49 v/v). The catalyst can be readily separated from the reaction mixture by fluorous extraction with FC-72 and repeatedly reused. The practical advantage offered by the fluorous catalyst is demonstrated by its sequential use in up to five different metathesis reactions. 相似文献
16.
Maity PK Kainz QM Faisal S Rolfe A Samarakoon TB Basha FZ Reiser O Hanson PR 《Chemical communications (Cambridge, England)》2011,47(46):12524-12526
The utilization of a monomer-on-monomer (MoM) intramolecular Mitsunobu cyclization reaction employing norbornenyl-tagged (Nb-tagged) reagents is reported for the synthesis of benzofused thiadiazepine-dioxides. Facile purification was achieved via ring-opening metathesis (ROM) polymerization initiated by one of three metathesis catalyst methods: (i) free metathesis catalyst, (ii) surface-initiated catalyst-armed silica, or (iii) surface-initiated catalyst-armed Co/C magnetic nanoparticles. 相似文献
17.
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
18.
Rix D Caijo F Laurent I Boeda F Clavier H Nolan SP Mauduit M 《The Journal of organic chemistry》2008,73(11):4225-4228
Three novel "boomerang" precatalysts bearing different aminocarbonyl functions are reported. Comparative kinetic studies show that this functional group allows for a control of the catalytic activity in metathesis transformations. The scope of the more active catalyst is investigated and shows a good tolerance to various substrates in ring-closing metathesis, enyne metathesis, and cross metathesis. ICP-MS analyses illustrate the good affinity of this catalyst for silica gel, as levels of Ru contamination lower than 6 ppm are detected in the final products. 相似文献
19.
20.
An assisted tandem catalytic transformation of diallyl amines and diallyl ethers into N-aryl pyrroles and furans, respectively, is described. The sequence relies on ring closing metathesis followed by dehydrogenation of the initially formed dihydropyrroles and dihydrofurans. Both steps are Ru-catalyzed, but the sequence requires only one precatalyst, because conversion of the metathesis catalyst into the dehydrogenation catalyst is achieved in situ, triggered by the oxidant tert-butyl hydroperoxide. 相似文献