- Light-Promoted Transfer of an Iridium Hydride in Alkyl Ether Cleavage
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A catalytic, light-promoted hydrosilylative cleavage reaction of alkyl ethers is reported. Initial studies are consistent with a mechanism involving heterolytic silane activation followed by delivery of a photohydride equivalent to a silyloxonium ion generated in situ. The catalyst resting state is a mixture of Cp*Ir(ppy)H (ppy = 2-phenylpyridine-κC,N) and a related hydride-bridged dimer. Trends in selectivity in substrate reduction are consistent with nonradical mechanisms for C-O bond scission. Irradiation of Cp*Ir(ppy)H with blue light is found to increase the rate of hydride delivery to an oxonium ion in a stoichiometric test. A comparable rate enhancement is found in carbonyl hydrosilylation catalysis, which operates through a related mechanism also involving Cp*Ir(ppy)H as the resting state.
- Fast, Caleb D.,Schley, Nathan D.
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supporting information
p. 3291 - 3297
(2021/10/12)
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- Synergistic Catalysis by Br?nsted Acid/Carbodicarbene Mimicking Frustrated Lewis Pair-Like Reactivity
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Carbodicarbene (CDC), unique carbenic entities bearing two lone pairs of electrons are well-known for their strong Lewis basicity. We demonstrate herein, upon introducing a weak Br?nsted acid benzyl alcohol (BnOH) as a co-modulator, CDC is remolded into a Frustrated Lewis Pair (FLP)-like reactivity. DFT calculation and experimental evidence show BnOH loosely interacting with the binding pocket of CDC via H-bonding and π-π stacking. Four distinct reactions in nature were deployed to demonstrate the viability of proof-of-concept as synergistic FLP/Modulator (CDC/BnOH), demonstrating enhanced catalytic reactivity in cyclotrimerization of isocyanate, polymerization process for L-lactide (LA), methyl methacrylate (MMA) and dehydrosilylation of alcohols. Importantly, the catalytic reactivity of carbodicarbene is uniquely distinct from conventional NHC which relies on only single chemical feature of nucleophilicity. This finding also provides a new spin in diversifying FLP reactivity with co-modulator or co-catalyst.
- Bai, Yuna,Chan, Yi-Chen,Chen, Hsing-Yin,Chen, Hsuan-Ying,Chen, Wen-Ching,Li, Chen-Yu,Ong, Tiow-Gan,Tseng, Mei-Chun,Wu, Ying-Yann,Yap, Glenn P. A.,Zhao, Lili
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supporting information
p. 19949 - 19956
(2021/08/03)
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- Hydrosilylation of carbonyls over electron-enriched Ni sites of intermetallic compound Ni3Ga heterogeneous catalyst
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Nanoparticulate intermetallic compound Ni3Ga supported on SiO2has emerged as a highly efficient catalyst for the hydrosilylation of carbonyls, such as aldehydes and ketones, at room temperature. Formation of electron-enriched Niviaal
- Takayama, Tomoaki,Kariya, Rio,Nakaya, Yuki,Furukawa, Shinya,Yamazoe, Seiji,Komatsu, Takayuki
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supporting information
p. 4239 - 4242
(2021/05/05)
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- Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation
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Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2NC6H4)Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2NC6H4}Bi{OP(NMe2)3}3][B(3,5-C6H3Cl2)4]2. These observations led us to generate dicationic organobismuth catalyst, [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si?H addition.
- Kannan, Ramkumar,Balasubramaniam, Selvakumar,Kumar, Sandeep,Chambenahalli, Raju,Jemmis, Eluvathingal D.,Venugopal, Ajay
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supporting information
p. 12717 - 12721
(2020/09/09)
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- Selective alkyl ether cleavage by cationic bis(phosphine)iridium complexes
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Catalysts capable of heterolytic silane activation have been successfully applied to the conversion of alkyl ethers to silyl ethers via C-O bond cleavage. The previously-reported cationic pincer-supported iridium complex for this transformation suffers fr
- Jones, Caleb A. H.,Schley, Nathan D.
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p. 1744 - 1748
(2019/02/20)
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- Pt-catalyzed O-silylation of oximes by tri-substituted organosilanes
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Silylated derivatives of oximes are important intermediates in organic synthesis, and have found application in the preparation of various nitrogen containing compounds including nitriles, amines, nitrones, and hydroxylamines. An efficient method for the
- Bhatt, Shreeja V.,Bhatt, Shreya V.,Fotie, Jean
-
supporting information
p. 1636 - 1639
(2019/06/04)
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- Carbonyl and olefin hydrosilylation mediated by an air-stable phosphorus(iii) dication under mild conditions
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The readily-accessible, air-stable Lewis acid [(terpy)PPh][B(C6F5)4]21 is shown to mediate the hydrosilylation of aldehydes, ketones, and olefins. The utility and mechanism of these hydrosilylations are considered.
- Andrews, Ryan J.,Chitnis, Saurabh S.,Stephan, Douglas W.
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supporting information
p. 5599 - 5602
(2019/05/21)
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- Organoaluminum cations for carbonyl activation
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In search of stable, yet reactive aluminum Lewis acids, we have isolated an organoaluminum cation, [(Me2NC6H4)2Al(C4H8O)2]+, coordinated with two labile tetrahydrofuran ligands. Its catalytic performance in aldehyde dimerization reveals turn-over frequencies reaching up to 6000 h-1, exceeding that of the reported main group catalysts. The cation is further demonstrated to catalyze hydroelementation of ketones. Mechanistic investigations reveal that aldehyde dimerization and ketone hydrosilylation occur through carbonyl activation.
- Kannan, Ramkumar,Chambenahalli, Raju,Kumar, Sandeep,Krishna, Athul,Andrews, Alex P.,Jemmis, Eluvathingal D.,Venugopal, Ajay
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supporting information
p. 14629 - 14632
(2019/12/11)
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- Metal-Free Catalytic Reductive Cleavage of Enol Ethers
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In contrast to the well-known reductive cleavage of the alkyl-O bond, the cleavage of the alkenyl-O bond is much more challenging especially using metal-free approaches. Unexpectedly, alkenyl-O bonds were reductively cleaved when enol ethers were reacted with Et3SiH and a catalytic amount of B(C6F5)3. Supposedly, this reaction is the result of a B(C6F5)3-catalyzed tandem hydrosilylation reaction and a silicon-assisted β-elimination. A mechanism for this cleavage reaction is proposed based on experiments and density functional theory (DFT) calculations.
- Chulsky, Karina,Dobrovetsky, Roman
-
supporting information
p. 6804 - 6807
(2018/11/02)
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- N-Heterocyclic Olefin Catalyzed Silylation and Hydrosilylation Reactions of Hydroxyl and Carbonyl Compounds
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N-Heterocyclic olefins (NHOs), the alkylidene derivatives of N-heterocyclic carbenes (NHCs), have recently emerged as a new family of promising organocatalysts with strong nucleophilicity and Br?nsted basicity. The development of a novel method is shown using NHOs as efficient promoters for the direct dehydrogenative silylation of alcohols or hydrosilylation of carbonyl compounds. Preliminary results of the first NHO-promoted asymmetric synthesis are also discussed.
- Kaya, U?ur,Tran, Uyen P.N.,Enders, Dieter,Ho, Junming,Nguyen, Thanh V.
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supporting information
p. 1398 - 1401
(2017/03/23)
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- Metal-Organic Frameworks Stabilize Mono(phosphine)-Metal Complexes for Broad-Scope Catalytic Reactions
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Mono(phosphine)-M (M-PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal-organic framework (MOF) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C-H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M-PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.
- Sawano, Takahiro,Lin, Zekai,Boures, Dean,An, Bing,Wang, Cheng,Lin, Wenbin
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supporting information
p. 9783 - 9786
(2016/08/19)
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- Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations
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Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods.
- Mehta, Meera,Holthausen, Michael H.,Mallov, Ian,Pérez, Manuel,Qu, Zheng-Wang,Grimme, Stefan,Stephan, Douglas W.
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p. 8250 - 8254
(2015/07/07)
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- Dehydrogenative coupling of alcohol with hydrosilane catalyzed by an iron complex
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Silane alcoholysis of triethylsilane (Et3SiH) with alcohol (ROH) with the help of CpFe(CO)2Me (1) has been achieved to produce triethylsilyl ether (ROSiEt3) under the thermal condition. For some alcohols, the iron complex
- Fukumoto, Kozo,Kasa, Michiho,Nakazawa, Hiroshi
-
p. 219 - 221
(2015/03/30)
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- Copper(I) complexes of mesoionic carbene: Structural characterization and catalytic hydrosilylation reactions
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Two series of different Cu(I)-complexes of "click" derived mesoionic carbenes are reported. Halide complexes of the type (MIC)CuI (with MIC = 1,4-(2,6-diisopropyl)-phenyl-3-methyl-1,2,3-triazol-5-ylidene (for 1b), 1-benzyl-3-methyl-4-phenyl-1,2,3-triazol-
- Hohloch, Stephan,Duecker, Fenja Leena,Van Meer, Margarethe Der,Sarkar, Biprajit
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p. 7379 - 7395
(2015/05/13)
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- Preparation of nano silica supported sodium hydrogen sulfate: As an efficient catalyst for the trimethyl, triethyl and t-butyldimethyl silylations of aliphatic and aromatic alcohols in solution and under solvent-free conditions
-
Nano silica supported sodium hydrogen sulfate has been prepared by mixing NaHSO4 with activated Nano silicagel. We wish to report a new method for the synthesis of trimethyl (TMS), triethyl (TES) and t-butyldimethyl silyl (TBS) ethers from benzylic, allylic, propargylic alcohols, phenols, naphtholes and some of phenolic drugs in the solution and under solvent-free conditions.
- Abri, Abdolreza,Ranjdar, Somayeh
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p. 929 - 934
(2014/10/16)
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- Rapid assessment of protecting-group stability by using a robustness screen
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An experimentally simple method has been developed to rapidly establish the stability of widely utilized silyl, acetal, and carbamate protecting groups to a given set of reaction conditions. Assessment of up to twelve protecting groups in a single experiment has been demonstrated. Evaluation of this protocol in two unrelated synthetic transformations suggests that this method can be used to select appropriate protecting groups in the design of synthetic routes.
- Collins, Karl D.,Ruehling, Andreas,Lied, Fabian,Glorius, Frank
-
supporting information
p. 3800 - 3805
(2014/04/03)
-
- Anionic and zwitterionic copper(i) complexes incorporating an anionic N-heterocyclic carbene decorated with a malonate backbone: Synthesis, structure and catalytic applications
-
The anionic malonate-derived N-heterocyclic carbenes (maloNHCs) react cleanly and rapidly with copper chloride to generate the anionic complexes of type [(maloNHC)CuCl]·Li, which crystallize in the solid state either in an oligomeric trimer arrangement or
- Cesar, Vincent,Barthes, Cecile,Farre, Yoann C.,Cuisiat, Stephane V.,Vacher, Bernard Y.,Brousses, Remy,Lugan, Noel,Lavigne, Guy
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p. 7373 - 7385
(2013/07/25)
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- Controlled hydrosilylation of carbonyls and imines catalyzed by a cationic aluminum alkyl complex
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The synthesis, characterization, and unprecedented catalytic activity of cationic aluminum alkyl complexes toward hydrosilylation are described. X-ray crystallographic analysis of Tp*AlMe2 (1) and [Tp*AlMe][I3] (3) revealed the prefe
- Koller, Juergen,Bergman, Robert G.
-
scheme or table
p. 2530 - 2533
(2012/06/04)
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- Tandem deuteration/hydrosilylation reactions catalyzed by a rhodium carbene complex under solvent-free conditions
-
The complex [Rh(ItBu)2HCl] has been shown to be an active catalyst in the hydrosilylation of carbonyl and imine complexes. This reactivity, combined with the previously reported H/D exchange catalyzed by these complexes allows for a
- Egbert, Jonathan D.,Nolan, Steven P.
-
supporting information; experimental part
p. 2794 - 2796
(2012/04/23)
-
- Probing the catalytic potential of chloro nitrosyl rhenium(i) complexes
-
The reduction of the mononitrosyl Re(ii) salt [NMe4] 2[ReCl5(NO)] (1) with zinc in acetonitrile afforded the Re(i) dichloride complex [ReCl2(NO)(CH3CN)3] (2). Subsequent ligand substitution reactions with PCy3, PiPr 3 and P(p-tolyl)3 afforded the bisphosphine Re(i) complexes [ReCl2(NO)(PR3)2(CH3CN)] (3, R = Cy a, iPr b, p-tolyl c) in good yields. The acetonitrile ligand in 3 is labile, permitting its replacement with H2 (1 bar) to afford the dihydrogen Re(i) complexes [ReCl2(NO)(PR3) 2(η2-H2)] (4, R = Cy a, iPr b). The catalytic activity of 2, 3 and 4 in hydrogen-related catalyses including dehydrocoupling of Me2NH·BH3, dehydrogenative silylation of styrenes, and hydrosilylation of ketones and aryl aldehydes were investigated, with the main focus on phosphine and halide effects. In the dehydrocoupling of Me2NH·BH3, the phosphine-free complex 2 exhibits the same activity as the bisphosphine-substituted systems. In the dehydrogenative silylation of styrenes, 3a and 4a bearing PCy3 ligands exhibit high catalytic activities. Monochloro Re(i) hydrides [Re(Cl)(H)(NO)(PR3)2(CH3CN)] (5, R = Cy a, iPr b) were proven to be formed in the initiation pathway. The phosphine-free complex 2 showed in dehydrogenative silylations even higher activity than the bisphosphine derivatives, which further emphasizes the importance of a facile phosphine dissociation in the catalytic process. In the hydrosilylation of ketones and aryl aldehydes, at least one rhenium-bound phosphine is required to ensure high catalytic activity.
- Jiang, Yanfeng,Blacque, Olivier,Berke, Heinz
-
experimental part
p. 2578 - 2587
(2011/05/03)
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- Rhodium-catalyzed, efficient deutero- and tritiosilylation of carbonyl compounds from hydrosilanes and deuterium or tritium
-
A cationic rhodium compound which is an active catalyst for both the hydrogen isotope exchange in hydrosilanes and the hydrosilylation of carbonyl compounds permits, in a one-flask, two-step procedure, efficient deutero- and tritiosilylations using SiEt3H under D2 (0.5 bar) or T2, at low catalyst loadings (0.1-0.5 mol %).
- Rubio, Miguel,Campos, Jesuus,Carmona, Ernesto
-
supporting information; experimental part
p. 5236 - 5239
(2011/12/15)
-
- Complexes: Synthesis, characterization and catalytic activities in reduction reactions and Click Chemistry. on the advantage of using well-defined catalytic systems
-
The preparation of three series of [(NHC)CuX] complexes (NHC = N-heterocyclic carbene, X = Cl, Br, or I) is reported. These syntheses are high yielding and only use readily available starting materials. The prepared complexes were spectroscopically and st
- Diez-Gonzalez, Silvia,Escudero-Adan, Eduardo C.,Benet-Buchholz, Jordi,Stevens, Edwin D.,Slawin, Alexandra M. Z.,Nolan, Steven P.
-
supporting information; experimental part
p. 7595 - 7606
(2010/09/16)
-
- Highly selective dehydrogenative silylation of alkenes catalyzed by rhenium complexes
-
Rhenium(I) complexes of type [ReBr2(L)(NO)(PR3) 2] (L = H2 (1), CH3CN (2), and ethylene (3); R = iPr (a) and cyclohexyl (Cy; b)) catalyze dehydrogenative silylation of alkenes in a highly selective ma
- Jiang, Yanfeng,Blacque, Olivier,Fox, Thomas,Freeh, Christian M.,Berke, Heinz
-
supporting information; experimental part
p. 2121 - 2128
(2009/09/30)
-
- A convenient and efficient rhenium-Catalyzed hydrosilylation of ketones and aldehydes
-
The easily available rhenium(I) complex [Re(CH3CN) 3Br2(NO)] catalyzes the homogeneous hydrosilylation of a great variety of organic carbonyl compounds (ketones and aldehydes). The reaction is quite sensitive to the solven
- Dong, Hailin,Berke, Heinz
-
experimental part
p. 1783 - 1788
(2011/02/25)
-
- Synthesis and characterization of [Cu(NHC)2]X Complexes: catalytic and mechanistic studies of hydrosilylation reactions
-
The preparation of two series of [Cu(NHC)2]X complexes (NHC = N-heterocyclic carbene, X = PF6 or BF4) in high yields from readily available materials is reported. These complexes have been spectroscopically and structurall
- Diez-Gonzalez, Silvia,Stevens, Edwin D.,Scott, Natalie M.,Petersen, Jeffrey L.,Nolan, Steven P.
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p. 158 - 168
(2008/09/18)
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- Cationic carboxylato complexes of dirhodium(II) with oxo thioethers: Catalysts for silane alcoholysis under homogeneous and liquid-liquid biphasic conditions
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A set of cationic dirhodium(II) complexes with oxo thioethers was prepared and employed as catalysts for the silane alcoholysis reaction. The complexes were found to be highly active under homogeneous conditions, both in the absence and in the presence of a solvent, including coordinating solvents such as N,N-dimethylformamide ; the catalysts could be conveniently employed in concentrations as low as 0.01 mol%, and a maximum TON of 30000 was recorded after 24 h. The same catalysts were also employed under liquid-liquid biphasic conditions with an ionic liquid as the catalyst-containing phase: comparable catalytic activity was observed under these conditions, and the catalyst-containing phase could be recovered and recycled. A chiral cationic dirhodium(II) complex was also prepared in the frame of this work; kinetic resolution of a racemic alcohol was attempted with this catalyst, unfortunately without success.
- Biffis, Andrea,Basato, Marino,Brichese, Marianna,Ronconi, Luca,Tubaro, Cristina,Zanella, Alessandra,Graiff, Claudia,Tiripicchio, Antonio
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p. 2485 - 2492
(2008/09/19)
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- Monocoordinating, compact phosphane immobilized on silica surface: Application to rhodium-catalyzed hydrosilylation of hindered ketones
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(Chemical Equation Presented) Activity without mobility: A compact trialkylphosphane, chemically immobilized on a silica gel surface (see picture), exhibited unique coordination behavior to form a 1:1 Rh/P complex. The monophosphane-{RhCl(cod)} species on
- Hamasaka, Go,Ochida, Atsuko,Hara, Kenji,Sawamura, Masaya
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p. 5381 - 5383
(2008/09/16)
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- Solventless silane alcoholysis catalyzed by recoverable dirhodium(II) perfluorocarboxylates
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We have developed a novel reaction protocol for the highly efficient and sustainable catalysis of the silane alcoholysis reaction. The catalysts of choice are dirhodium(II) perfluorocarboxylates bearing long perfluoroalkyl chains, which are easily prepare
- Biffis, Andrea,Braga, Mirko,Basato, Marino
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p. 451 - 458
(2007/10/03)
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- Rate enhancement with a bowl-shaped phosphane in the rhodium-catalyzed hydrosilylation of ketones
-
Up to 154-fold rate enhancement (see picture) and higher yields are achieved with the bowl-shaped triarylphosphane ligand P(tm-tp)3 compared with common phosphane ligands in Rh-catalyzed hydrosilylation of ketones. The superior performance of P(tm-tp)3 over the similar P(tp)3 is apparently related to the deeper bowl formed by the methyl-bearing terphenyl substituents in the former.
- Niyomura, Osamu,Tokunaga, Makoto,Obora, Yasushi,Iwasawa, Tetsuo,Tsuji, Yasushi
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p. 1287 - 1289
(2007/10/03)
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- Fluorous biphasic catalysis with dirhodium(II) perfluorocarboxylates: Selective silylation of alcohols under fluorous biphasic conditions
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Dirhodium(II) perfluorocarboxylates bearing C7-C13 perfluoroalkyl chains have been prepared and used as catalysts under fluorous biphasic conditions. They were found to be active and recyclable catalysts for the silylation of alcohols with triethylsilane.
- Biffis, Andrea,Castello, Erika,Zecca, Marco,Basato, Marino
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p. 10391 - 10394
(2007/10/03)
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- A Novel B(C6F5)3-Catalyzed Reduction of Alcohols and Cleavage of Aryl and Alkyl Ethers with Hydrosilanes
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The primary alcohols 1a-e and ethers 4a-d were effectively reduced to the corresponding hydrocarbons 2 by HSiEt3 in the presence of catalytic amounts of B(C6F5)3. To the best of our knowledge, this is the first example of catalytic use of Lewis acid in the reduction of alcohols and ethers with hydrosilanes. The secondary alkyl ethers 4j,k enabled cleavage and/or reduction under similar reaction conditions to produce either the silyl ethers 3m-n or the corresponding alcohol 5a upon subsequent deprotection with TBAF. It was found that the secondary alcohols 1g-i and tertiary alcohol 1j, as well as the tertiary alkyl ether 4l, did not react with HSiEt3/(B(C6F5)3 reducing reagent at all. The following relative reactivity order of substrates was found: primary ? secondary > tertiary. A plausible mechanism for this nontraditional Lewis acid catalyzed reaction is proposed.
- Gevorgyan, Vladimir,Rubin, Michael,Benson, Sharonda,Liu, Jian-Xiu,Yamamoto, Yoshinori
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p. 6179 - 6186
(2007/10/03)
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- A novel reduction of alcohols and ethers with a HSiEt3/catalytic B(C6F5)3 system
-
The primary alcohols 1a-d and ethers 4a-b were effectively reduced into the corresponding hydrocarbons 2 by HSiEt3 in the presence of catalytic amounts of B(C6F5)3. The secondary alkyl ethers 4g,h underwent cleavage and/or reduction under similar reaction conditions to produce either the silyl ether 3k or the corresponding alcohol 5b upon subsequent deprotection with TBAF. The secondary alcohols (1g,h) and tertiary alcohol 1i, as well as tertiary alkyl ether 4i, did not react with the HSiEt3/(B(C6F5)3 reducing reagent at all. The following relative reactivity order of substrates was found: primary>>secondary>tertiary. The methyl aryl ethers 4c-e and alkyl aryl ether 4f were smoothly deprotected to give the corresponding silyl ethers 3b,h-j in nearly quantitative isolated yields.
- Gevorgyan, Vladimir,Liu, Jian-Xiu,Rubin, Michael,Benson, Sharonda,Yamamoto, Yoshinori
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p. 8919 - 8922
(2007/10/03)
-
- Reduction of Carbonyl Compounds with Hydrosilanes on Solid Acid and Solid Bases
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Hydrosilylations of carbonyl compounds were performed on the surfaces of solid acids and bases.Strongly acidic clays efficiently catalyzed the reduction of aldehydes and ketones with trialkylsilanes (e.g.Et3SiH) to afford symmetrical ethers or hydrocarbons, depending upon the characters of substituents around carbonyl groups.Reduction-resistant ketone like 4,4'-dimethoxybenzophenone was found to be reduced with Et3SiH under the catalytic influence of the highly acidic clay.In contrast, trialkoxysilanes (e.g. (EtO)3SiH) became labile in contact with solid base like hydroxyapatite, reducing a variety of carbonyl compounds to yield alkoxy(triethoxy)silane in good yields.It was revealed that besides fluoride salts, solid bases bearing mild basicity and relatively large surface areas can activate the trialkoxysilane enough for reduction of carbonyl functions.
- Onaka, Makoto,Higuchi, Katsumi,Nanami, Hiroyuki,Izumi, Yusuke
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p. 2638 - 2645
(2007/10/02)
-
- HYDROSILYLATION OF CARBONYL COMPOUNDS CATALYZED BY SOLID ACIDS AND BASES
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Hydrosilylation of carbonyl compounds with hydrosilane is efficiently catalyzed by inorganic solid acids and bases such as Fe(3+) ion-exchanged montmorillonite and hydroxyapatite (Ca10(PO4)6(OH)2) at reaction temperatures between 25 and 90 deg C.Enones ar
- Izumi, Yusuke,Nanami, Hiroyuki,Higuchi, Katsumi,Onaka, Nakoto
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p. 4741 - 4744
(2007/10/02)
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- Ionic Hydrogenation with Organosilanes under Acid-Free Conditions. Synthesis of Ethers, Alkoxysilanes, Thioethers, and Cyclic Ethers via Organosylil Iodide and Triflate Catalyzed Reductions of Carbonyl Compounds and Their Derivatives
-
The general ether synthesis method based on the trialkylsilane/trialkylsilyl iodide or triflate reagent system has been extended to the syntheses of alkoxysilanes from ketones, tetrahydrofurans and tetrahydropyrans from dicarbonyl compounds, and thioethers by reductive cleavage of O-silylhemithioacetals.
- Sassaman, Mark B.,Prakash, G. K. Surya,Olah, George A.
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p. 3771 - 3780
(2007/10/02)
-
- TRIETHYLSILYLATION OF HYDROXYL GROUPS WITH A KETENE TRIETHYLSILYL ACETAL - 2-METHYL-1-TRIETHYLSILYLOXY-1-METHOXYPROPENE
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A convenient O-triethylsilylation with dimethylketene triethylsilyl methyl acetal (1), which is prepared in excellent yield by catalytic hydrosilylation of methyl metacrylate is reported.Primary alcohols react readily at room temperature.Hindered alcohols
- Yoshii, Eiichi,Takeda, Kei
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p. 4586 - 4588
(2007/10/02)
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- RHODIUM(II) COMPLEXES AS HYDROSILYLATION AND HYDROGENATION CATALYSTS
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Two phosphine-rhodium(II) complexes, bis(tris-o-tolylphosphine)dichlororhodium(II) and bis(tricyclohexylphosphine)dichlororhodium(II), have been found to be active catalysts for the hydrosilylation of a variety of organic substrates, and, in conjunction with triethylaluminum, to be hydrogenation catalysts.
- Howe, J.P.,Lung, K.,Nile, Terence A.
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p. 401 - 406
(2007/10/02)
-