- Mechanism of the dehydrogenative silylation of alcohols catalyzed by cationic gold complexes: An experimental and theoretical study
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The catalytic activity both of cationic [(XDPP)Au][X] (XDPP=bis-2,5- diphenylphosphole xantphos X=BF4) and of the isolated gold hydride complex [(XDPP)2Au2H][OTf] in the dehydrogenative silylation process is presented. A p
- Labouille, Stephanie,Escalle-Lewis, Aurelie,Jean, Yves,Mezailles, Nicolas,Leafloch, Pascal
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- Use of Silylated Formiates as Hydrosilane Equivalents
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The present invention relates to a method for preparing organic compounds of formula (I) by reaction between a silylated formiate of formula (II) and an organic compound in the presence of a catalyst and optionally of an additive. The invention also relates to use of the method for preparing organic compounds of formula (I) for the preparation of reagents for fine chemistry and for heavy chemistry, as well as in the production of vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, and pesticides.
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- Chemoselective Deoxygenation of 2° Benzylic Alcohols through a Sequence of Formylation and B(C6F5)3-Catalyzed Reduction
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A sequence of formylation and B(C6F5)3-catalyzed reduction of the resulting formate with Et3SiH enables the chemoselective deoxygenation of secondary benzylic alcohols. Primary benzylic and tertiary non-benzylic alcohols are not reduced by this protocol. The formyl group fulfills a double role as activator and self-sacrificing protecting group. The deoxygenation of these formates is fast and can be carried out in the presence of other potentially reducible groups. Neighboring-group participation was found in the deoxygenation of certain diol motifs.
- Oestreich, Martin,Richter, Sven C.
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supporting information
p. 2103 - 2106
(2021/07/22)
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- Cationic Dirhodium Complexes Bridged by 2-Phosphinopyridines Having an Exquisitely Positioned Axial Shielding Group: A Molecular Design for Enhancing the Catalytic Activity of the Dirhodium Core
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This report describes a strategy to create highly electrophilic dirhodium catalysts. The electrophilicity of lantern-Type dirhodium complexes is generally decreased by the coordination of a ligand to the axial site, which often causes a reduction in the catalytic activity. We designed and synthesized a series of cationic dirhodium complexes bridged by 2-diarylphosphinopyridines having a bulky 2,4,6-Triisopropylphenyl (Tip) group that can prevent the attack of external molecules to the closest axial site. Theoretical calculations indicated that the Tip group weakly interacts with the axial site but hardly reduces the electrophilicity of the dirhodium core. The complexes served as excellent catalyst precursors for the dehydrogenative silylation of alcohols using hydrosilanes under mild conditions and a low metal loading, producing the silyl ethers in higher yields in comparison to conventional dirhodium complexes.
- Ohnishi, Ryuhei,Ohta, Hidetoshi,Mori, Shigeki,Hayashi, Minoru
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p. 2678 - 2690
(2021/07/31)
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- Hydrosilylation of Carbonyls Catalyzed by Hydridoborenium Borate Salts: Lewis Acid Activation and Anion Mediated Pathways
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The electronically unsaturated three-coordinated hydridoborenium cations [LBH]+[HB(C6F5)3]-(1) and [LBH]+[B(C6F5)4]-(2), supported by a bis(phosphinimino)amide ligand, were found to be excellent catalysts for hydrosilylation of a range of aliphatic and ar
- Rawat, Sandeep,Bhandari, Mamta,Porwal, Vishal Kumar,Singh, Sanjay
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supporting information
p. 7195 - 7203
(2020/05/18)
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- Controlling Sugar Deoxygenation Products from Biomass by Choice of Fluoroarylborane Catalyst
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The feedstocks from biomass are defined and limited by nature, but through the choice of catalyst, one may change the deoxygenation outcome. We report divergent but selective deoxygenation of sugars with triethylsilane (TESH) and two fluoroarylborane catalysts, B(C6F5)3 and B(3,5-CF3)2C6H3)3 (BAr3,5-CF3). To illustrate, persilylated 2-deoxyglucose shows exocyclic C-O bond cleavage/reduction with the less sterically congested BAr3,5-CF3, whereas endocyclic C-O bond cleavage/reduction predominates with the more Lewis acidic B(C6F5)3. Chiral furans and linear polyols can be selectively synthesized depending on the catalysts. Mechanistic studies demonstrate that the resting states of these catalysts are different.
- Seo, Youngran,Lowe, Jared M.,Gagné, Michel R.
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p. 6648 - 6652
(2019/08/26)
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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
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supporting information
p. 1636 - 1639
(2019/06/04)
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- Iron-Catalyzed Silylation of Alcohols by Transfer Hydrosilylation with Silyl Formates
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An iron catalyst is shown for the first time to promote transfer hydrosilylation with silyl formates and is utilized for the silylation of alcohols. Attractive features of this protocol include the use of an earth-abundant transition-metal catalyst, mild reaction conditions, and the release of gases as the only byproducts (H 2 and CO 2).
- Godou, Timothé,Chauvier, Clément,Thuéry, Pierre,Cantat, Thibault
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p. 2473 - 2477
(2017/10/26)
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- Silylation of O-H bonds by catalytic dehydrogenative and decarboxylative coupling of alcohols with silyl formates
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The silylation of O-H bonds is a useful methodology in organic synthesis and materials science. While this transformation is commonly achieved by reacting alcohols with reactive chlorosilanes or hydrosilanes, we show herein for the first time that silylformates HCO2SiR3 are efficient silylating agents for alcohols, in the presence of a ruthenium molecular catalyst.
- Chauvier, Clément,Godou, Timothé,Cantat, Thibault
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p. 11697 - 11700
(2017/11/03)
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- A Versatile Iridium(III) Metallacycle Catalyst for the Effective Hydrosilylation of Carbonyl and Carboxylic Acid Derivatives
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A versatile iridium(III) metallacycle catalysed rapidly and selectively the reduction of a large array of challenging esters and carboxylic acids as well as various ketones and aldehydes. The reactions proceeded in high yields at room temperature by hydrosilylation followed by desilylation. Although the reactions of various aldehydes and ketones resulted exclusively in alcohols, the hydrosilylation of esters led to alcohols or ethers, depending on the type of substrate. Regarding the carboxylic acids, again the nature of the reagent controlled the outcome of the hydrosilylation reaction, either alcohols or aldehydes being formed.
- Corre, Yann,Rysak, Vincent,Trivelli, Xavier,Agbossou-Niedercorn, Francine,Michon, Christophe
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supporting information
p. 4820 - 4826
(2017/09/07)
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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-Free Ammonium Iodide Catalyzed Oxidative Dehydrocoupling of Silanes with Alcohols
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An ammonium iodide catalyzed direct oxidative coupling of silanes with alcohols to give various alkoxysilane derivatives was discovered. tert -Butyl hydroperoxide proved to be an efficient oxidant for this transformation. Attractive features of this protocol include its transition-metal-free nature and the mild reaction conditions.
- Yuan, Yan-Qin,Kumar, Pailla Santhosh,Guo, Sheng-Rong
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supporting information
p. 1620 - 1623
(2017/08/11)
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- Selective Hydrosilylation of Esters to Aldehydes Catalysed by Iridium(III) Metallacycles through Trapping of Transient Silyl Cations
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The combination of an iridium(III) metallacycle and 1,3,5-trimethoxybenzene catalyses rapidly and selectively the reduction of esters to aldehydes at room temperature with high yields through hydrosilylation followed by hydrolysis. The ester reduction involves the trapping of transient silyl cations by the 1,3,5-trimethoxybenzene co-catalyst, supposedly by formation of an arenium intermediate whose role was addressed by DFT calculations.
- Corre, Yann,Rysak, Vincent,Capet, Frédéric,Djukic, Jean-Pierre,Agbossou-Niedercorn, Francine,Michon, Christophe
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supporting information
p. 14036 - 14041
(2016/09/21)
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- Unprecedented organocatalytic reduction of lignin model compounds to phenols and primary alcohols using hydrosilanes
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The first metal-free reduction of lignin model compounds is described. Using inexpensive Et3SiH, PMHS and TMDS hydrosilanes as reductants, α-O-4 and β-O-4 linkages are reduced to primary alcohols and phenols under mild conditions using B(C6F5)3 as an efficient catalyst. The Royal Society of Chemistry.
- Feghali, Elias,Cantat, Thibault
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p. 862 - 865
(2014/01/06)
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- Ruthenium catalyzed selective hydrosilylation of aldehydes
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A chemoselective hydrosilylation method for aldehydes is developed using a ruthenium catalyst [(Ru(p-cymene)Cl2)2] and triethylsilane; a mono hydride bridged dinuclear complex [{(η6-p- cymene)RuCl}2(μ-H-μ-Cl)] a
- Chatterjee, Basujit,Gunanathan, Chidambaram
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supporting information
p. 888 - 890
(2014/01/06)
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- N-heterocyclic carbene organocatalysts for dehydrogenative coupling of silanes and hydroxyl compounds
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Go organic! N-Heterocyclic carbene (NHC) 1,3-diisopropyl-4,5- dimethylimidazol-2-ylidene (IiPr) has been found to be an efficient and selective catalyst for the dehydrogenative coupling of a wide range of silanes and hydroxyl groups to form Si-O bonds under mild and solvent-free conditions (see scheme). Mechanistic studies indicated that the activation of hydroxyl groups by the NHC is the most plausible initial step for the process. Copyright
- Gao, Dongjing,Cui, Chunming
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supporting information
p. 11143 - 11147
(2013/09/02)
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- Hydrosilylation of epoxides catalyzed by a cationic η1- silane iridium(iii) complex
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Cationic silane complex 2, catalyzes the hydrosilylation of epoxides and cyclic ethers to give the silyl-protected alcohols, regioselectively. A mechanistic study shows that the epoxide undergoes isomerization to the ketone, followed by hydrosilylation.
- Park, Sehoon,Brookhart, Maurice
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supporting information; experimental part
p. 3643 - 3645
(2011/05/04)
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- Silylation of primary alcohols with recyclable ruthenium catalyst and hydrosilanes
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The silylation of primary alcohols was achieved using hydrosilanes and a recyclable ruthenium catalyst without additives under mild conditions. Notably, this catalyst system is effective for the silylation of alcohols having haloaryl groups, which were in
- Kim, Sungjin,Kwon, Min Serk,Park, Jaiwook
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supporting information; experimental part
p. 4573 - 4575
(2010/09/14)
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- The chemoselective and efficient deprotection of silyl ethers using trimethylsilyl bromide
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An efficient and chemoselective cleavage of silyl ethers (primary, secondary and aromatic) by using catalytic quantities of trimethylsilyl bromide (TMSBr) in methanol is reported. A wide range of alkyl silyl ethers such as TBS, TIPS, and TBDPS can be chemoselectively cleaved in high yield in the presence of aryl silyl ethers. The deprotection of silyl esters was also achieved employing catalytic quantities of TMSBr. The Royal Society of Chemistry 2008.
- Shah, Syed Tasadaque A.,Guiry, Patrick J.
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experimental part
p. 2168 - 2172
(2009/02/01)
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- SURFACE MODIFIED ORGANIC·INORGANIC HYBRID GLASS, PROTECTING GROUP INDUCED ALCOHOL OR ITS DERIVATIVE AND PRODUCING METHOD THEREOF
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Disclosed are a protected alcohol or derivative thereof, a surface- modified organic-inorganic hybrid glass, and preparation methods thereof. More specifically, disclosed are a protected alcohol or derivative thereof and a surface-modified organic-inorganic hybrid glass, which are prepared by allowing a silane compound, having vinyl or a vinyl derivative, to react with an alcohol or derivative thereof or with an organic-inorganic hybrid glass, in the presence of an acid catalyst, a transition metal catalyst and an organic solvent, so as to introduce an organic group thereto even at room temperature, as well as preparation methods thereof. The disclosed invention allows a functional group to be effectively introduced into alcohol or a derivative thereof or into an organic-inorganic hybrid glass, not only high temperatures but also room temperature, and thus is highly effective in introducing compounds having a thermally sensitive functional group, for example, natural compounds or proteins. Also, the invention makes it possible to introduce various organic groups and to separate and purify organic macromolecule-bonded organosilane compounds using a silica gel column so as to effectively introduce large organic functional groups to inorganic materials. Accordingly, the invention is highly useful in the chemical industry.
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Page/Page column 31-33
(2010/11/28)
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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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- Gold(I)-phosphine catalyst for the highly chemoselective dehydrogenative silylation of alcohols
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(Chemical Equation Presented) A gold(I) complex of Xantphos AuCl(xantphos) catalyzes the dehydrogenative silylation of alcohols with high chemoselectivity and solvent tolerance. It is selective for the silylation of hydroxyl groups in the presence of alke
- Ito, Hajime,Takagi, Katsuhiro,Miyahara, Takahiro,Sawamura, Masaya
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p. 3001 - 3004
(2007/10/03)
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- Co2(CO)8 CATALYZED REACTIONS OF STYRENE OXIDE WITH TRIALKYLSILANES
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The dicobalt octacarbonyl catalyzed reaction of styrene oxide with trialkylsilanes yields a mixture of 1-phenyl-2-trialkylsiloxyethane and Z- and E-1-phenyl-2-trialkylsiloxyethene.The ratio of these products can be controlled.
- Kang, Kyung-Tae,Weber, William P.
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p. 5415 - 5416
(2007/10/02)
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- 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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