- Immobilisation of an ionically tagged Hoveyda catalyst on a supported ionic liquid membrane: An innovative approach for metathesis reactions in a catalytic membrane reactor
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This study aimed at developing an innovative strategy to recycle homogeneous olefin metathesis catalysts by the combination of complementary green processes, namely organic solvent nanofiltration coupled with ionic liquid advantages. The immobilisation of
- Keraani,Rabiller-Baudry,Fischmeister,Bruneau
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Read Online
- Water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration
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Here, we report water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration. The copolymer, denoted as PAAT, was synthesised via copolymerisation of acrylamide (AM), acrylic acid (AA) and N,N-diallyl-4-methylbenzene
- Gou, Shaohua,Yin, Ting,Liu, Kun,Guo, Qipeng
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Read Online
- One-pot chemoenzymatic reactions in water enabled by micellar encapsulation
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The use of micellar conditions to enable one-pot reactions involving both transition metal and enzymatic catalysts is reported. Representative enzymatic transformations under micellar conditions are unaffected by the presence of non-ionic surfactants, including designer surfactants such as TPGS-750-M. Furthermore, the presence of enzymes has a negligible effect on transition metal catalysis under micellar conditions in water. Finally, three one-pot chemoenzymatic reactions in water are reported in which the micelle-forming surfactant TPGS-750-M is a crucial factor for reaction efficiency.
- Adams, Nicholas P.,Bushi, Jurgen,Hastings, Courtney J.,Kolb, Samuel J.
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supporting information
p. 6187 - 6193
(2020/10/18)
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- Synthesis of N -Sulfonyl- and N -Acylpyrroles via a Ring-Closing Metathesis/Dehydrogenation Tandem Reaction
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N -Sulfonyl- and N -acylpyrroles were synthesized via olefin ring-closing metathesis of diallylamines and in situ oxidative aromatization in the presence of the ruthenium Grubbs catalyst and a suitable copper catalyst. In the presence of Cu(OTf) 2/s
- Chen, Weiqiang,Li, Hui-Jing,Liu, Ying,Nan, Xiang,Wu, Yan-Chao,Zhang, Yin-Lin
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supporting information
p. 3651 - 3666
(2019/09/30)
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- Aminoxyl-Catalyzed Electrochemical Diazidation of Alkenes Mediated by a Metastable Charge-Transfer Complex
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We report the development of a new aminoxyl radical catalyst, CHAMPO, for the electrochemical diazidation of alkenes. Mediated by an anodically generated charge-transfer complex in the form of CHAMPO-N3, radical diazidation was achieved across a broad scope of alkenes without the need for a transition metal catalyst or a chemical oxidant. Mechanistic data support a dual catalytic role for the aminoxyl serving as both a single-electron oxidant and a radical group transfer agent.
- Siu, Juno C.,Parry, Joseph B.,Lin, Song
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supporting information
p. 2825 - 2831
(2019/02/14)
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- Nickel(0)-Catalyzed N-Allylation of Amides and p-Toluenesulfonamide with Allylic Alcohols under Neat and Neutral Conditions
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Nickel(0)-catalyzed direct N-allylation of amides and p-toluenesulfonamide with allylic alcohols took place in the presence of Ni0–diphosphine complexes. The corresponding N-allylated (and/or N,N-diallylated) products were obtained in moderate to high yields under neutral conditions.
- Azizi, Mohamed Salah,Edder, Youssef,Karim, Abdallah,Sauthier, Mathieu
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p. 3796 - 3803
(2016/08/16)
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- Iodine-catalyzed expeditious synthesis of sulfonamides from sulfonyl hydrazides and amines
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A new synthesis of sulfonamides has been developed via an iodine-catalyzed sulfonylation of amines with arylsulfonyl hydrazides. This metal-free strategy employs readily accessible and easy to handle starting materials, catalysts and oxidants, and can be easily conducted under mild conditions, providing a convenient access to a wide range of sulfonamides in moderate to excellent yields within a short reaction time.
- Yotphan, Sirilata,Sumunnee, Ladawan,Beukeaw, Danupat,Buathongjan, Chonchanok,Reutrakul, Vichai
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p. 590 - 597
(2016/01/12)
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- Ligand Control of E/Z Selectivity in Nickel-Catalyzed Transfer Hydrogenative Alkyne Semireduction
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A nickel-catalyzed transfer hydrogenative alkyne semireduction protocol that can be applied to both internal and terminal alkynes using formic acid and Zn as the terminal reductants has been developed. In the case of internal alkynes, the (E)- or (Z)-olefin isomer can be accessed selectively under the same reaction conditions by judicious inclusion of a triphos ligand.
- Richmond, Edward,Moran, Joseph
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p. 6922 - 6929
(2015/10/05)
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- Origins of initiation rate differences in ruthenium olefin metathesis catalysts containing chelating benzylidenes
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A series of second-generation ruthenium olefin metathesis catalysts was investigated using a combination of reaction kinetics, X-ray crystallography, NMR spectroscopy, and DFT calculations in order to determine the relationship between the structure of the chelating o-alkoxybenzylidene and the observed initiation rate. Included in this series were previously reported catalysts containing a variety of benzylidene modifications as well as four new catalysts containing cyclopropoxy, neopentyloxy, 1-adamantyloxy, and 2-adamantyloxy groups. The initiation rates of this series of catalysts were determined using a UV/vis assay. All four new catalysts were observed to be faster-initiating than the corresponding isopropoxy control, and the 2-adamantyloxy catalyst was found to be among the fastest-initiating Hoveyda-type catalysts reported to date. Analysis of the X-ray crystal structures and computed energy-minimized structures of these catalysts revealed no correlation between the Ru-O bond length and Ru-O bond strength. On the other hand, the initiation rate was found to correlate strongly with the computed Ru-O bond strength. This latter finding enables both the rationalization and prediction of catalyst initiation through the calculation of a single thermodynamic parameter in which no assumptions about the mechanism of the initiation step are made.
- Engle, Keary M.,Lu, Gang,Luo, Shao-Xiong,Henling, Lawrence M.,Takase, Michael K.,Liu, Peng,Houk,Grubbs, Robert H.
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supporting information
p. 5782 - 5792
(2015/05/20)
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- A medium fluorous Grubbs-Hoveyda 2nd generation catalyst for phase transfer catalysis of ring closing metathesis reactions
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A fluorous Grubbs-Hoveyda metathesis catalyst supported on Teflon powder, that readily moves between the solid phase (Teflon) and the liquid phase (DMF) was prepared. By modulating the hydrophobicity of the reaction medium at the end of the reaction, the supported catalyst could be recovered by simple filtration even though the catalyst existed in a homogeneous state during the reaction. In RCM reactions, the catalyst could be reused up to three times with only a slight loss in reactivity with each subsequent cycle.
- Kobayashi, Yuki,Inukai, Sae,Kondo, Natsuki,Watanabe, Tomoko,Sugiyama, Yuya,Hamamoto, Hiromi,Shioiri, Takayuki,Matsugi, Masato
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supporting information
p. 1363 - 1366
(2015/03/04)
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- Hydroxy chalcogenide-promoted Morita-Baylis-Hillman Alkylation reaction: Intermolecular applications with alkyl halides as electrophiles
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Hydroxysulfides acted as catalysts to promote the Morita-Baylis-Hillman alkylation reaction of cyclohexenones and dihydropyridinones. The procedure worked efficiently with a variety of halides as electrophiles. Side reactions were in competition with the MBH alkylation, but fine-tuning the reaction conditions minimized their occurence.
- Gradillas, Ana,Belmonte, Efres,Da Silva, Rondes Ferreira,Perez-Castells, Javier
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p. 1935 - 1941
(2014/04/03)
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- Hydroxy Chalcogenide-Promoted Morita-Baylis-Hillman Alkylation Reaction: Intermolecular Applications with Alkyl Halides as Electrophiles
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Hydroxysulfides acted as catalysts to promote the Morita-Baylis-Hillman alkylation reaction of cyclohexenones and dihydropyridinones. The procedure worked efficiently with a variety of halides as electrophiles. Side reactions were in competition with the
- Gradillas, Ana,Belmonte, Efres,Da Silva, Rondes Ferreira,Prez-Castells, Javier
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p. 1935 - 1941
(2015/10/05)
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- Tandem ring-closing metathesis/transfer hydrogenation: Practical chemoselective hydrogenation of alkenes
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An operationally simple chemoselective transfer hydrogenation of alkenes using ruthenium metathesis catalysts is presented. Of great practicality, the transfer hydrogenation reagents can be added directly to a metathesis reaction and effect hydrogenation of the product alkene in a single pot at ambient temperature without the need to seal the vessel to prevent hydrogen gas escape. The reduction is applicable to a range of alkenes and can be performed in the presence of aryl halides and benzyl groups, a notable weakness of Pd-catalyzed hydrogenations. Scope and mechanistic considerations are presented.
- Connolly, Timothy,Wang, Zhongyu,Walker, Michael A.,McDonald, Ivar M.,Peese, Kevin M.
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supporting information
p. 4444 - 4447
(2015/01/09)
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- Low catalyst loading in ring-closing metathesis reactions
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An efficient procedure is described for ring-closing metathesis reactions. A conversion of 95 % for diethyl diallylmalonate in dilute solution could be achieved within a few minutes, reaching TOF=4173min-1, with very low loading of commercially available Ru catalysts that contained unsaturated NHC ligands. In general, only 50 to 250ppm of the catalyst is required to achieve near-quantitative conversion into a broad variety of 5-16-membered heterocyclic compounds. The practicality of this procedure was illustrated in the synthesis of 5-8-membered N-tert-butoxycarbonyl (N-Boc)- and N-para-toluenesulfonyl (N-Ts)-protected cyclic amines and 9-16-membered lactones. The synthesis of macrocyclic proline-based lactams required slightly higher catalyst loadings. Along with monocyclic products, oligomeric byproducts, mostly cyclodimers, were isolated and characterized. Getting some closure: An efficient procedure is described for ring-closing metathesis reactions in which only 50 to 250ppm of catalyst is required to effect almost-quantitative conversion into a broad range of 5-16-membered heterocyclic compounds. The practicality of this procedure was illustrated in the synthesis of 5-8-membered N-protected cyclic amines, 9-16-membered lactones, and 11-16-membered proline-based lactams. Copyright
- Kadyrov, Renat
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supporting information
p. 1002 - 1012
(2013/02/23)
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- Rhodium-catalyzed asymmetric hydroarylation of 3-pyrrolines giving 3-arylpyrrolidines: Protonation as a key step
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A hydroxorhodium complex coordinated with (R)-segphos was found to catalyze the hydroarylation of 3-pyrrolines with arylboroxines under neutral conditions to give 3-arylpyrrolidines with high enantioselectivity in high yields.
- So, Chau Ming,Kume, Satoshi,Hayashi, Tamio
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supporting information
p. 10990 - 10993
(2013/08/23)
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- Generation of stoichiometric ethylene and isotopic derivatives and application in transition-metal-catalyzed vinylation and enyne metathesis
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Ethylene is one of the most important building blocks in industry for the production of polymers and commodity chemicals. 13C- and D-isotope-labeled ethylenes are also valuable reagents with applications ranging from polymer-structure determination, reaction-mechanism elucidation to the preparation of more complex isotopically labeled compounds. However, these isotopic derivatives are expensive, and are flammable gases, which are difficult to handle. We have developed a method for the controlled generation of ethylene and its isotopic variants including, for the first time, fully isotopically labeled ethylene, from simple alkene precursors by using Ru catalysis. Applying a two-chamber reactor allows both the synthesis of ethylene and its immediate consumption in a chemical transformation permitting reactions to be performed with only stoichiometric amounts of this two carbon olefin. This was demonstrated in the Ni-catalyzed Heck reaction with aryl triflates and benzyl chlorides, as well as Ru-mediated enyne metathesis. Why more when less works! A method for the controlled generation of ethylene including the fully isotopically labeled derivative is described, as well as their use in three transition-metal-catalyzed reactions. Applying a two-chamber reactor, only stoichiometric amounts of ethylene are required, which allows the simple installment of deuterium and 13C in the product (see scheme).
- Min, Geanna K.,Bjerglund, Klaus,Kramer, Soren,Gogsig, Thomas M.,Lindhardt, Anders T.,Skrydstrup, Troels
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supporting information
p. 17603 - 17607
(2014/01/06)
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- Assisted tandem catalytic RCM-aromatization in the synthesis of pyrroles and furans
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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.
- Schmidt, Bernd,Krehl, Stefan,Jablowski, Eric
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supporting information; experimental part
p. 5119 - 5130
(2012/08/07)
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- Stereoselective alkene isomerization over one position
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Although controlling both the position of the double bond and E:Z selectivity in alkene isomerization is difficult, 1 is a very efficient catalyst for selective mono-isomerization of a variety of multifunctional alkenes to afford >99.5% E-products. Many reactions are complete within 10 min at room temperature. Even sensitive enols and enamides susceptible to further reaction can be generated. Catalyst loadings in the 0.01-0.1 mol% range can be employed. E-to-Z isomerization of the product from diallyl ether was only -6 times as fast as its formation, showing the extremely high kinetic selectivity of 1.
- Larsen, Casey R.,Grotjahn, Douglas B.
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supporting information; experimental part
p. 10357 - 10360
(2012/08/08)
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- An atom efficient route to N-aryl and N-alkyl pyrrolines by transition metal catalysis
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The synthesis of N-aryl, N-tosyl, and N-alkyl pyrrolines from allyl alcohols and amines has been developed. The reaction sequence includes a palladium-catalyzed allylation step in which non-manipulated allyl alcohol is used to generate the diallylated amine in good to excellent yield. An excess of allyl alcohol was necessary for efficient diallylation of the amine, where the excess alcohol could be recycled three times. For aryl and tosyl amines, Pd[P(OPh)3]4 was used and for benzyl and alkyl amines a catalytic system comprising Pd(OAc)2, PnBu3, and BEt3 was used. Both the electronic properties and the steric influence of the amine affected the efficiency of the allylation. The isolated diallylated amines were transformed into their corresponding pyrrolines by ring-closing metathesis catalyzed by (H2IMes)(PCy3)Cl 2RuCHPh in good to excellent yield. A one-pot reaction was developed in which aniline was transformed into the corresponding pyrroline without isolating the diallylated intermediate. This one-pot reaction was successfully scaled-up to 1 mL of aniline in which the N-phenyl pyrroline was isolated in 95% yield. The versatility of the reaction in which 3-methyl-1-phenyl pyrroline was prepared in two-steps was demonstrated.
- Sawadjoon, Supaporn,Samec, Joseph S. M.
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scheme or table
p. 2548 - 2554
(2011/05/04)
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- Direct use of allylic alcohols in the allylation of sulfonylimidates
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We have developed catalytic allylation reactions of sulfonylimidates using allylic alcohols as allylating reagents. Stoichiometric amounts of neither activators nor bases are required in this reaction.
- Matsubara, Ryosuke,Masuda, Koichiro,Nakano, Jyunya,Kobayashi, Sh
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supporting information; scheme or table
p. 8662 - 8664
(2011/01/03)
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- Palladium(II)-catalyzed domino reaction of 2-(1-alkynyl)-2-alken-1-ones with nucleophiles: Scope, mechanism and synthetic application in the synthesis of 3,4-fused bicyclic tetrasubstituted furans
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Described herein is the development of a palladium(II)-catalyzed two- or three-component reaction of 2-(1-alkynyl)-2-alken-1-ones with nucleophiles and allylic chlorides. Various types of nucleophiles such as O-, N-, C-based nucleophiles and olefin-tether
- Xiao, Yuanjing,Zhang, Junliang
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supporting information; experimental part
p. 617 - 629
(2009/10/25)
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- Magnetic nanoparticle-supported Hoveyda-Grubbs catalysts for ring-closing metathesis reactions
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Magnetically recyclable Hoveyda-Grubbs catalyst can be readily assembled using magnetic nanoparticles as support, and this catalyst combines convenient recyclability and excellent activity on ring-closing metathesis (RCM) reactions.
- Che, Chao,Li, Wenzhao,Lin, Shengyue,Chen, Jiwei,Zheng, Jie,Wu, Jiun-Chen,Zheng, Qunxiong,Zhang, Guoqing,Yang, Zhen,Jiang, Biwang
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supporting information; experimental part
p. 5990 - 5992
(2010/11/16)
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- Carbon-carbon bond forming reactions with substrates absorbed non-covalently on a cellulose chromatography paper support
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Reactions and purifications, including carbon-carbon bond forming reactions, can be carried out on a cellulose support on which the substrates are non-covalently absorbed. The Royal Society of Chemistry.
- Hacon, Jonathon,Morris, Amanda,Johnston, Michael J.,Shanahan, Stephen E.,Barker, Mike D.,Inglis, Graham G. A.,Macdonald, Simon J. F.
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p. 625 - 627
(2007/10/03)
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- An ionic liquid-tagged second generation Hoveyda-Grubbs ruthenium carbene complex as highly reactive and recyclable catalyst for ring-closing metathesis of di-, tri- and tetrasubstituted dienes
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A second generation Hoveyda-Grubbs ruthenium carbene complex bearing an ionic liquid tag was prepared and shown to be a highly reactive catalyst for the ring-closing metathesis of di-, tri- and tetrasubstituted diene and enyne substrates in minimally ioni
- Yao, Qingwei,Sheets, Matthew
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p. 3577 - 3584
(2007/10/03)
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- Triethylsilane-indium(III) chloride system as a radical reagent
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(Chemical Equation Presented) A novel generation method of indium hydride (Cl2InH) was found by the transmetalation of InCl3 with Et3SiH. In the intramolecular cyclization of enynes, the previously reported system (NaBH4-InCl3) has a problem of side reactions with the coexistent borane. In contrast, the problem was solved by the presented system, which affords effective hydroindation of alkynes.
- Hayashi, Naoki,Shibata, Ikuya,Baba, Akio
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p. 4981 - 4983
(2007/10/03)
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- Cycloisomerization promoted by the combination of a ruthenium-carbene catalyst and trimethylsilyl vinyl ether, and its application in the synthesis of heterocyclic compounds: 3-Methylene-2,3-dihydroindoles and 3-methylene-2,3- dihydrobenzofurans
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Substituted N and O heterocycles have been synthesized by the cycloisomerization of dienes using a ruthenium-carbene catalyst. The products obtained with and without trimethylsilyl vinyl ether differ (see scheme, Cy = cyclohexyl, Mes = 2,4,6-trimethylphenyl, Ts = p-toluenesulfonyl).
- Terada, Yukiyoshi,Arisawa, Mitsuhiro,Nishida, Atsushi
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p. 4063 - 4067
(2007/10/03)
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- Radical transfer hydrosilylation/cyclization using silylated cyclohexadienes
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(matrix presented) A new method for mild metal-free hydrosilylation is described. Silylated cyclohexadienes are used as radical transfer hydrosilylating reagents for various double and triple bonds. A trialkylsilane is transferred from a cyclohexadiene mo
- Amrein, Stephan,Timmermann, Andreas,Studer, Armido
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p. 2357 - 2360
(2007/10/03)
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- Initiation of radical cyclisation reactions using dimanganese decacarbonyl. A flexible approach to preparing 5-membered rings
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Photolysis of dimanganese decacarbonyl [Mn2(CO)10] using visible light produces the manganese pentacarbonyl radical [Mn(CO)5] which reacts with organohalides to form carbon-centred radicals. Efficient halogen-atom abstract
- Gilbert, Bruce C.,Kalz, Wilhelm,Lindsay, Chris I.,McGrail, P. Terry,Parsons, Andrew F.,Whittaker, David T. E.
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p. 1187 - 1194
(2007/10/03)
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- Co-catalyst dependent cycloisomerization or ring closing metathesis of α,ω-dienes catalyzed by arene ruthenium complex with side-arm alcohol
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Cycloisomerization and ring closing metathesis of some α,ω-dienes were catalyzed by a cationic arene ruthenium chelate complex [Ru{η6:η1-Ph(CH2) 3OH}(PCy3)Cl]BF4 (1a) in the presence of triethylamine and phenylacetylene, respectively, as co-catalysts. Analogous catalyst systems employing arene ruthenium cations without the side arm alcohol functional group showed lower efficiencies.
- Miyaki, Yoshiharu,Onishi, Takafumi,Ogoshi, Sensuke,Kurosawa, Hideo
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p. 135 - 139
(2007/10/03)
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- Palladium(0)-catalyzed allylation of highly acidic and non-nucleophilic arenesulfonamides, sulfamide, and cyanamide. I.
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Arenesulfonamides, sulfamide, and cyanamide are efficiently allylated using allylic carbonates under Pd(0)-catalysis. N-Arenesulfonyl-2,5- dihydropyrroles are obtained by ruthenium-mediated ring closing metathesis of the corresponding N-diallylated compounds. A stereochemical study of the reactions of ethyl cis-(5-methyl-2-cyclohexenyl) carbonate with 2,4,6- triisopropylphenylsulfonamide was performed, clean overall retention of configuration being found with bidentate phosphines.
- Cerezo, Silvia,Cortes, Jordi,Moreno-Manas, Marcial,Pleixats, Roser,Roglans, Anna
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p. 14869 - 14884
(2007/10/03)
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- REACTION OF ALKANE- AND ARENESULFONAMIDES WITH ALLYLIC ELECTROPHILES, CATALYZED BY TRANSITION METAL COMPLEXES
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The reactions of N-methyl-, N-phenyl-, N-amyl-, and N-allyl-p-toluenesulfonamides and the corresponding butanesulfonamides and also of unsubstituted p-toluenesulfonamide with allyl alcohols, ethers, esters, amines, sulfides, and sulfones, catalyzed by the
- Kunakova, R. V.,Sirazova, M. M.,Dzhemilev, U. M.
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p. 746 - 752
(2007/10/02)
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- Direct N-Allylation of Amides with 2-Allylisourea Catalyzed by Palladium(0)
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Direct N-allylation of amides catalyzed by palladium(0) complexes took place under neutral conditions by the use of 2-allylisourea as the allylating agent.
- Inoue, Yoshio,Taguchi, Masaaki,Hashimoto, Harukichi
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p. 2721 - 2722
(2007/10/02)
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