- Method for synthesizing furan compound through one-step reaction of ketone and alpha chloroketone
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The invention provides a method for preparing a polysubstituted furan compound by taking alpha-chloroketone and methyl ketone or cyclic ketone as raw materials through one-step reaction under the action of slightly excessive tetraisopropyl titanate and a solvent-free condition. The method comprises the following steps: under the protection of inert gas, stirring and heating a reaction mixture of methyl ketone or cyclic ketone, alpha-chloroketone and p-toluenesulfonic acid, adding tetraisopropyl titanate for reaction, and separating and purifying the obtained reaction mixture after the reaction is finished to obtain the polysubstituted furan compound. The synthesis method provided by the invention has the advantages of easily available raw materials, low cost, simple operation and easy control, no solvent, good substrate universality and functional group compatibility, and is suitable for industrial mass production.
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Paragraph 0003
(2022/01/10)
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- ORGANIC REACTIONS CARRIED OUT IN AQUEOUS SOLUTION IN THE PRESENCE OF A HYDROXYALKYL(ALKYL)CELLULOSE OR AN ALKYLCELLULOSE
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The present invention relates to a method of carrying out an organic reaction in aqueous solution in the presence of a hydroxyalkyl(alkyl)cellulose or an alkylcellulose.
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Page/Page column 239; 240
(2017/08/21)
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- Direct β-arylation of furans with aryl iodides catalyzed by dinuclear palladium complexes
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Dinuclear palladium complexes formed by a chelate-bridging ligand showed β-selectivity in the direct arylation of furans with iodoarenes. In contrast, the arylation using PPh3 or bpy as ligands gave α-arylfurans as major products. The arylation
- Goto, Takahiro,Kato, Hayate,Tsukada, Naofumi
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p. 2222 - 2228
(2017/12/12)
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- Sustainable Micellar Gold Catalysis - Poly(2-oxazolines) as Versatile Amphiphiles
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The application of five polymer amphiphiles in the gold-catalyzed allene cycloisomerizations under aqueous micellar conditions is described. The polymers were prepared by ring-opening cationic polymerization based on poly(2-methyl-2-oxazoline) as hydrophilic segment and different hydrocarbon- or fluorocarbon-based hydrophobic segments. The catalytic activity in the gold-catalyzed allene cyclization is strongly dependent on the type of gold precursor, the salt concentration in the bulk aqueous medium, and the concentration of the polymeric amphiphile. Best results were obtained with 2 mol% of gold(III) bromide, 1 mM of amphiphile and 5 M sodium chloride, affording over 80% yield for different heterocyclic products. The catalyst system is also suitable for the dehydrative cyclization of acetylenic diols to furans. Moreover, successful catalyst recycling was demonstrated in three consecutive runs when using optimized extraction conditions.
- Lempke, Linda,Ernst, Andrea,Kahl, Fabian,Weberskirch, Ralf,Krause, Norbert
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supporting information
p. 1491 - 1499
(2016/05/19)
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- Direct C-H Arylation of Heteroarenes with Copper Impregnated on Magnetite as a Reusable Catalyst: Evidence for CuO Nanoparticle Catalysis in Solution
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A reusable copper-based catalyst system was employed for the direct arylation of electron-rich heteroarenes. Under mild and operationally simple reaction conditions good yields and selectivities were obtained using diaryliodonium salts as coupling partners. A combination of experimental methods including kinetic studies, filtration tests, and a series of analytical tools (TXRF, ICP-MS, SEM, XPS, TEM, EFTEM) provide evidence for catalytically active soluble nanoparticles formed from an amorphous heterogeneous precursor. Mechanistic studies hint at a redox-neutral process which promotes counterion dissociation from the diaryliodonium salt by a copper(II) oxide species.
- Vásquez-Céspedes, Suhelen,Chepiga, Kathryn M.,M?ller, Nadja,Sch?fer, Andreas H.,Glorius, Frank
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p. 5954 - 5961
(2016/09/09)
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- Successively recycle waste as catalyst: A one-pot wittig/1,4-reduction/paal-knorr sequence for modular synthesis of substituted furans
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A one-pot tandem Wittig/conjugate reduction/Paal-Knorr reaction is reported for the synthesis of di- or trisubstituted furans. This novel sequence first demonstrates the possibility of successively recycling waste from upstream steps to catalyze downstream reactions.
- Chen, Long,Du, Yi,Zeng, Xing-Ping,Shi, Tao-Da,Zhou, Feng,Zhou, Jian
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p. 1557 - 1560
(2015/03/30)
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- Deep eutectic solvents: Biorenewable reaction media for Au(i)-catalysed cycloisomerisations and one-pot tandem cycloisomerisation/Diels-Alder reactions
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Cycloisomerisation reactions of (Z)-enynols into furans can be conveniently performed, for the first time, in the eutectic mixture 1ChCl/2Gly as a solvent and under standard bench conditions (at room temperature and under air) by using the new bis(iminoph
- Vidal,Merz,García-álvarez
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p. 3870 - 3878
(2015/07/15)
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- Leveraging the micellar effect: Gold-catalyzed dehydrative cyclizations in water at room temperature
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The first examples of gold-catalyzed cyclizations of diols and triols to the corresponding hetero- or spirocycles in an aqueous medium are presented. These reactions take place within nanomicelles, where the hydrophobic effect is operating, thereby driving the dehydrations, notwithstanding the surrounding water. By the addition of simple salts such as sodium chloride, reaction times and catalyst loadings can be significantly decreased.
- Minkler, Stefan R. K.,Isley, Nicholas A.,Lippincott, Daniel J.,Krause, Norbert,Lipshutz, Bruce H.
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supporting information
p. 724 - 726
(2014/03/21)
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- Ruthenium-catalyzed allylation-cyclization reactions of cyclic 1,3-dicarbonyl compounds with 1-vinyl propargyl alcohols
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Ruthenium-catalyzed allylation-cyclization reactions of cyclic 1,3-dicarbonyl compounds with 1-vinyl propargyl alcohols that lead to diverse carbo- or heterocyclic products in a one-pot cascade process are reported. These mechanistically distinct reactions are catalyzed by a single ruthenium(0) complex that contains a redox-coupled dienone ligand. The reaction pathway strongly depends on the substrate substitution pattern, which determines the mode of activation of the 1-vinyl propargyl alcohol. The environmentally benign process, which generates water as the only waste product, is of wide scope and allows the atom-economic synthesis of highly functionalized furans, pyrans, and spirocarbocycles. Ring-producing expert: Ru complexes of redox-coupled cyclopentadienone ligands catalyze various allylation-cyclization reactions of cyclic 1,3-dicarbonyl compounds with 1-vinyl propargyl alcohols through strikingly distinct modes of activation to afford highly functionalized furans, pyrans, and spirocarbocycles (see scheme). Copyright
- Jonek, Anita,Berger, Stefanie,Haak, Edgar
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p. 15504 - 15511
(2013/01/15)
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- Ruthenium-catalyzed functionalization of pyrroles and indoles with propargyl alcohols
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Several ruthenium-catalyzed atom-economic transformations of propargyl alcohols with pyrroles or indoles leading to alkylated, propargylated, or annulated heteroaromatics are reported. The mechanistically distinct reactions are catalyzed by a single ruthenium(0) complex containing a redox-coupled dienone ligand. The mode of activation regarding the propargyl alcohols determines the reaction pathway and depends on the alcohols' substitution pattern. Secondary substrates form alkenyl complexes by a 1,2-hydrogen shift, whereas the transformation of tertiary substrates involves allenylidene intermediates. 1-Vinyl propargyl alcohols are converted by a cascade allylation/cyclization sequence. The environmentally benign processes are of broad scope and allow the selective synthesis of highly functionalized pyrroles and indoles generating water as the only waste product. Copyright
- Thies, Nora,Hrib, Cristian G.,Haak, Edgar
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supporting information; experimental part
p. 6302 - 6308
(2012/06/18)
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- Chemistry by nanocatalysis: First example of a solid-supported RAPTA complex for organic reactions in aqueous medium
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A ruthenium-arene-PTA (RAPTA) complex has been supported for the first time on an inorganic solid, that is, silica-coated ferrite nanoparticles. The resulting magnetic material proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentration, environmentally friendly water as a reaction medium, with no use at all of organic solvent during or after the reactions, and microwaves as an alternative energy source renders the synthetic processes reported herein "truly" green and sustainable. RAPTA's delight: A nano-RAPTA complex supported on silica-coated ferrite nanoparticles proved to be a general, very efficient and easily reusable catalyst for three synthetically useful organic transformations; selective nitrile hydration, redox isomerization of allylic alcohols, and heteroannulation of (Z)-enynols. The use of low metal concentrations, water as a reaction medium, and microwaves as an energy source renders these processes green and sustainable.
- García-Garrido, Sergio E.,Francos, Javier,Cadierno, Victorio,Basset, Jean-Marie,Polshettiwar, Vivek
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experimental part
p. 104 - 111
(2012/01/06)
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- Palladium-catalyzed cycloisomerization of (Z)-enynols into furans using green solvents: Glycerol vs. water
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Heteroannulation reactions of (Z)-2-en-4-yn-1-ol derivatives into furans can be conveniently performed in water and glycerol using cis-[PdCl 2(DAPTA)2] as catalyst. Higher activities were observed in an aqueous medium, but catalyst r
- Francos, Javier,Cadierno, Victorio
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experimental part
p. 1552 - 1555
(2010/11/20)
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- Iridium(I)-catalyzed coupling of (Z)-2-En-4-yn-1-ols with activated alkynes: A new synthetic route to 7-oxanorbornadienes
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Taking advantage of the ability shown by the iridium(I) dimer [{Ir(μ-Cl)(COD)}2] to promote the cycloisomerization of (Z)-enynols into furans, an unprecedented synthetic route to 7-oxanorbornadienes has been developed just by performing the cat
- Diaz-Alvarez, Alba E.,Crochet, Pascale,Cadierno, Victorio
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experimental part
p. 2427 - 2431
(2010/12/25)
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- Metal-catalyzed 1,2-shift of diverse migrating groups in allenyl systems as a new paradigm toward densely functionalized heterocycles
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A general, mild, and efficient 1,2-migration/cycloisomerization methodology toward multisubstituted 3-thio-, seleno-, halo-, aryl-, and alkyl-furans and pyrroles, as well as fused heterocycles, valuable building blocks for synthetic chemistry, has been developed. Moreover, regiodivergent conditions have been identified for C-4 bromo- and thio-substituted allenones and alkynones for the assembly of regioisomeric 2-hetero substituted furans selectively. It was demonstrated that, depending on reaction conditions, ambident substrates can be selectively transformed into furan products, as well as undergo selective 6-exo-dig or Nazarov cyclizations. Our mechanistic investigations have revealed that the transformation proceeds via allenylcarbonyl or allenylimine intermediates followed by 1,2-group migration to the allenyl sp carbon during cycloisomerization. It was found that 1,2-migration of chalcogens and halogens predominantly proceeds via formation of irenium intermediates. Analogous intermediate can also be proposed for 1,2-aryl shift. Furthermore, it was shown that the cycloisomerization cascade can be catalyzed by Bransted acids, albeit less efficiently, and commonly observed reactivity of Lewis acid catalysts cannot be attributed to the eventual formation of proton. Undoubtedly, thermally induced or Lewis acid-catalyzed transformations proceed via intramolecular Michael addition or activation of the enone moiety pathways, whereas certain carbophilic metals trigger carbenoid/oxonium type pathway. However, a facile cycloisomerization in the presence of cationic complexes, as well as observed migratory aptitude in the cycloisomerization of unsymmetrically disubstituted aryl- and alkylallenes, strongly supports electrophilic nature for this transformation. Full mechanistic details, as well as the scope of this transformation, are discussed.
- Dudnik, Alexander S.,Sromek, Anna W.,Rubina, Marina,Kim, Joseph T.,Kel'in, Alexander V.,Gevorgyan, Vladimir
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p. 1440 - 1452
(2008/10/09)
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- An efficient furan synthesis using heterogeneous catalysis
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A wide variety of 3-alkyne-1,2-diols have been found to undergo exceptionally clean 5-endo-dig cyclisations followed by dehydration at ambient temperature to give the corresponding furans in essentially quantitative yields when exposed to 10 mol % of 10%
- Hayes, Simon J.,Knight, David W.,Menzies, Melanie D.,O'Halloran, Mark,Tan, Wen-Fei
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p. 7709 - 7712
(2008/03/30)
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- Metal-catalyzed [1,2]-alkyl shift in allenyl ketones: Synthesis of multisubstituted furans
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(Chemical Equation Presented) Even fused furans can be prepared by cycloisomerization of substituted allenyl ketones. The cascade reaction involves a [1,2]-migration of alkyl or aryl groups in allenyl ketones as the key step. Facile reaction in the presence of cationic complexes, as well as migratory aptitude in the cycloisomerization of unsymmetrically substituted allenes, strongly supports an electrophilic mechanism for this transformation.
- Dudnik, Alexander S.,Gevorgyan, Vladimir
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p. 5195 - 5197
(2008/03/27)
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- METHODS FOR THE SYNTHESIS OF HETEROAROMATIC COMPOUNDS
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Methods of making heteroaromatic compounds comprising a 5- membered ring, and dihydro forms thereof, by a metal catalysed 5-endo-cyclisation of alkynes (acetylenes) are disclosed. The methods involve the use of a catalyst comprising a silver salt, more preferably a silver (I) salt, which is employed as a heterogeneous catalyst for the cyclisation reaction. The methods can produce different types of heteroaromatic compounds and are capable of producing highly substituted products, i.e. products in which the 5-membered ring is disubstituted, trisubstituted or, with further simple reactions, tetrasubstituted. The methods described herein generally the advantages that they use conditions and reagents that are benign, cheap and flexible and amenable to scale up, and in which the only by-product is water.
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Page/Page column 35
(2008/06/13)
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- Ring-opening of tertiary cyclopropanols derived from β-diketones
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The ring-opening reaction of 1,2-disubstituted cyclopropanols, prepared from β-diketones, mediated by Cu(NO3)2, p-TsOH, and NaOH is reported. The Cu(II)-mediated ring-opening of cyclopropanols gave α-methylene-γ-diketones in good yie
- Li, Le-Zhen,Xiao, Bin,Guo, Qing-Xiang,Xue, Song
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p. 7762 - 7771
(2007/10/03)
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- A general and facile synthesis of substituted furans by palladium- catalyzed cycloisomerization of (Z)-2-en-4-yn-1-ols
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A general and facile synthesis of furans, based on Pd(II)-catalyzed cycloisomerization of (Z)-2-en-4-yn-1-ols, is described. Cycloisomerization reactions are carried out at 25-100 °C in the presence of a very simple catalytic system, consisting of K2PdI4, under essentially neutral conditions. This new methodology is very versatile and can be applied to the synthesis of a variety of substituted furans, including particularly fragile, naturally occurring furans such as rosefuran. Efficient synthetic approaches for the regioselective synthesis of suitably substituted (Z)-2-en-4-yn-1-ols have been developed.
- Gabriele,Salerno,Lauria
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p. 7687 - 7692
(2007/10/03)
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- An efficient synthesis of 2,3,5-trisubstituted furans from α,β- unsaturated ketones
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A simple, regioselective synthesis of 2,3,5-trisubstituted furans is described. Conjugate addition of alkynylboronates to α,β-unsaturated ketones, followed by acid-catalyzed cyclization of the resulting γ-alkynyl ketones affords trisubstituted furans in 3197% overall yields.
- Brown, Catherine D.,Chong, J. Michael,Shen, Lixin
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p. 14233 - 14242
(2007/10/03)
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- An efficient and general synthesis of furan-2-acetic esters by palladium-catalyzed oxidative carbonylation of (Z)-2-En-4-yn-l-ols
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A variety of (Z)-2-en-4-yn-l-ols have been carbonylated under oxidative conditions to give substituted furan-2-acetic esters in good yields. The cyclization-alkoxycarbonylation process occurs in alcoholic media at 50-70 °C and under 100 atm pressure of a 9:1 mixture of carbon monoxide and air in the presence of catalytic amounts of PdI2 in conjunction with KI. The proposed reaction pathway involves the in situ isomerization of the initially formed (£)-2-[(alkoxycarbonyl)methylene]-2, 5-dihydrofuran species, which in some cases have been isolated and shown to be the intermediates.
- Gabriele, Bartolo,Salerno, Giuseppe,De Pascali, Francesca,Costa, Mirco,Chiusoli, Gian Paolo
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p. 7693 - 7699
(2007/10/03)
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- A new and efficient synthesis of rosefuran. A general synthesis of furans by palladium-catalysed cycloisomerization of (Z)-2-en-4-yn-1-ols
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(Z)-3,7-Dimethylocta-2,6-dien-4-yn-1-ol, readily available from (Z)-3-methylpent-2-en-4-yn-1-ol, undergoes cycloisomerization in the presence of catalytic amounts of K2PdI4 to give rosefuran in high yield.
- Gabriele, Bartolo,Salerno, Giuseppe
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p. 1083 - 1084
(2007/10/03)
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- Novel synthesis of furan-2-acetic esters by palladium-catalysed oxidative cyclization-alkoxycarbonylation of (Z)-2-En-4-yn-1-ols
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Furan-2-acetic esters are obtained in good yields by direct oxidative cyclization-alkoxycarbonylation lation of (Z)-2-en-4-yn-1-ols. bearing both an alkyl or an aryl substituent a to the hydroxy group. in the presence of catalytic amounts of palladium iod
- Gabriele, Bartolo,Salerno, Giuseppe,De Pascali, Francesca,Sciano, Giuseppe Tomasi,Costa, Mirco,Chiusoli, Gian Paolo
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p. 6877 - 6880
(2007/10/03)
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- Synthesis of Furans by Cyclization of 2-En-4-yn-1-ols in the Presence of Ruthenium and Palladium Catalysts
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Substituted furans have been synthesized in the presence of ruthenium catalysts under neutral and mild conditions via cyclization of primary and secondary enynols of type (Z)-HCC-C(Me)=CH-CH(R)OH containing a terminal triple bond.The intramolecular addition of the hydroxy group to the triple bond of internal (Z)-enynols is also possible upon palladium catalysis.
- Seiller, Benedicte,Bruneau, Christian,Dixneuf, Pierre H.
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p. 13089 - 13102
(2007/10/02)
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- Novel ruthenium-catalysed synthesis of furan derivatives via intramolecular cyclization of hydroxy enynes
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Furans containing a functional group at C(5) are obtained under neutral conditions by selective cyclization of (Z)-pent-2-en-4-yn-1-ols in the presence of RuCl2(PPh3)(p-cymene) as catalyst precursor.
- Seiller,Bruneau,Dixneuf
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p. 493 - 494
(2007/10/02)
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