- Anodic oxidation of 2-alkyl-2-trialkylsilyl-1, 3-dithianes a facile preparation of acylsilanes
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Acylsilanes can easily be prepared by the anodic oxidation of 2-alkyl-2-trialkylsilyl-1, 3-dithianes with a platinum anode in wet acetonitrile. This electrochemical reaction provides a general and convenient access to aroyl, saturated and α, β-unsaturated
- Suda, Kohji,Watanabe, Jun-Ichi,Takanami, Toshikatsu
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Read Online
- Synthesis of aryl and alkyl acylsilanes using trimethyl(tributylstannyl)silane
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Palladium catalyzed coupling of acid chlorides and trimethyl(tribuhfistannyl)silane proves to be a convenient method for the preparation of both aromatic and aliphatic acylsilanes.
- Geng, Feng,Maleczka Jr., Robert E.
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Read Online
- Visible-Light Mediated Tryptophan Modification in Oligopeptides Employing Acylsilanes
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A method for the selective tryptophan modification and labelling of tryptophan-containing peptides is described. Photoirradiation of acylsilanes generates reactive siloxycarbenes which undergo H?N-insertion into the indole moiety of tryptophan to give stable silyl protected hemiaminals. This method is successfully applied to chemically modify various tryptophan containing oligopeptides. The method enables the selective introduction of alkynes to peptides that are eligible for further alkyne-azide click chemistry. In addition, the dansyl fluorophore can be conjugated to a peptide using this approach.
- Reimler, Jannik,Studer, Armido
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supporting information
p. 15392 - 15395
(2021/10/04)
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- Chemoselective Amide-Forming Ligation Between Acylsilanes and Hydroxylamines Under Aqueous Conditions
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We report the facile amide-forming ligation of acylsilanes with hydroxylamines (ASHA ligation) under aqueous conditions. The ligation is fast, chemoselective, mild, high-yielding and displays excellent functional-group tolerance. Late-stage modifications of an array of marketed drugs, peptides, natural products, and biologically active compounds showcase the robustness and functional-group tolerance of the reaction. The key to the success of the reaction could be the possible formation of the strong Si?O bond via a Brook-type rearrangement. Given its simplicity and efficiency, this ligation has the potential to unfold new applications in the areas of medicinal chemistry and chemical biology.
- Deng, Xingwang,Zhou, Guan,Tian, Jing,Srinivasan, Rajavel
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supporting information
p. 7024 - 7029
(2020/12/29)
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- Visible-Light-Induced Catalyst-Free Carboxylation of Acylsilanes with Carbon Dioxide
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Intermolecular carbon-carbon bond formation between acylsilanes and carbon dioxide (CO2) was achieved by photoirradiation under catalyst-free conditions. In this reaction, siloxycarbenes generated by photoisomerization of the acylsilanes added to the C═O bond of CO2 to give α-ketocarboxylates, which underwent hydrolysis to afford α-ketocarboxylic derivatives in good yields. Control experiments suggest that the generated siloxycarbene is likely to be from the singlet state (S1) of the acylsilane and the addition to CO2 is not in a concerted manner.
- Fan, Zhengning,Yi, Yaping,Chen, Shenhao,Xi, Chanjuan
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supporting information
p. 2303 - 2307
(2021/04/05)
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- Controllable one-pot synthesis for scaffold diversity: Via visible-light photoredox-catalyzed Giese reaction and further transformation
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This study presents a controllable one-pot synthesis for constructing valuable scaffolds (alcohols, 2,3-dihydrofurans, α-cyano-γ-butyrolactones, and γ-butyrolactones) via a visible-light photoredox-catalyzed Giese reaction and further transformation. This
- Nam, Su Been,Khatun, Nilufa,Kang, Young Woo,Park, Boyoung Y.,Woo, Sang Kook
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supporting information
p. 2873 - 2876
(2020/03/19)
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- Ruthenium-Catalyzed Brook Rearrangement Involved Domino Sequence Enabled by Acylsilane-Aldehyde Corporation
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A ruthenium-catalyzed [1,2]-Brook rearrangement involved domino sequence is presented to prepare highly functionalized silyloxy indenes with atomic- and step-economy. This domino reaction is triggered by acylsilane-directed C-H activation, and the aldehyde controlled the subsequent enol cyclization/Brook Rearrangement other than β-H elimination. The protocol tolerates a broad substitution pattern, and the further synthetic elaboration of silyloxy indenes allows access to a diverse range of interesting indene and indanone derivatives.
- Lu, Xiunan,Zhang, Jian,Xu, Liangyao,Shen, Wenzhou,Yu, Feifei,Ding, Liyuan,Zhong, Guofu
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supporting information
p. 5610 - 5616
(2020/07/24)
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- Preparation of Functionalized Acylsilanes by Diol Cleavage of Cyclic 1,2-Dihydroxysilanes
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We report a study on diol cleavage of cyclic 1,2-dihydroxysilanes for the preparation of functionalized acylsilanes. Sodium periodate turned out to be an efficient reagent for this transformation, resulting in good to excellent yields. The method is chara
- Zimdars, Patrick,B?hlig, Kristin,Metz, Peter
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p. 6163 - 6167
(2019/08/20)
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- Synthesis of Acylsilanes via Catalytic Dedithioacetalization of 2-Silylated 1,3-Dithianes with 30% Hydrogen Peroxide
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Acylsilanes were obtained efficiently from dedithioacetalization of 2-silylated 1,3-dithianes using 30% hydrogen peroxide catalyzed by iron(III) acetylacetonate-sodium iodide. The use of niobium(V) chloride as a catalyst instead of iron(III) acetylacetonate was also effective, except in synthesizing some acyltrimethylsilanes.
- Kirihara, Masayuki,Suzuki, Satoshi,Ishihara, Naohiro,Yamazaki, Kento,Akiyama, Tomomi,Ishizuka, Yuki
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p. 2009 - 2014
(2017/04/26)
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- Oxidative [1,2]-Brook Rearrangements Exploiting Single-Electron Transfer: Photoredox-Catalyzed Alkylations and Arylations
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Oxidative [1,2]-Brook rearrangements via hypervalent silicon intermediates induced by photoredox-catalyzed single-electron transfer have been achieved, permitting the formation of reactive radical species that can engage in alkylations and arylations.
- Deng, Yifan,Liu, Qi,Smith, Amos B.
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supporting information
p. 9487 - 9490
(2017/07/24)
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- Enantioselective Synthesis of Chiral 3-Substituted-3-silylpropionic Esters via Rhodium/Bisphosphine-Thiourea-Catalyzed Asymmetric Hydrogenation
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We have successfully developed the asymmetric hydrogenation of β-silyl-α,β-unsaturated esters to prepare chiral 3-substituted-3-silylpropionic ester products catalyzed by rhodium/bisphosphine-thiourea (ZhaoPhos) with excellent results (up to 97% yield, >99% ee, 1500 TON). Moreover, our hydrogenation products can be efficiently converted to other important organic molecules, such as chiral ethyl (R)-3-hydroxy-3-phenylpropanoate or (R)-3-[dimethyl(phenyl)silyl]-3-phenylpropanoic acid. (Figure presented.).
- Zhang, Zongpeng,Han, Zhengyu,Gu, Guoxian,Dong, Xiu-Qin,Zhang, Xumu
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supporting information
p. 2585 - 2589
(2017/08/16)
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- DENTAL COMPOSITION
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The present invention relates to a dental composition comprising a specific polymerization initiator system comprising a compound having an acylsilyl- or acylgermanyl-group. The present invention also relates the use of the compound having an acylsilyl- o
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Page/Page column 54
(2017/05/14)
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- DENTAL COMPOSITION
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Dental composition comprising (a) a homogeneous phase comprising monomer combinations (i) and (ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii), or comprising monomer (iii), wherein (i) represents one or more compounds having one or more radical
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Page/Page column 62-63
(2017/11/10)
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- Intermolecular Schmidt reaction of alkyl azides with acyl silanes
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The first intermolecular Schmidt reaction of alkyl azides with acyl silanes has been designed and realized, producing a range of amides with absolute site selectivity in good to excellent yields. The mechanism of the conversion has been proposed, and the reaction exhibits scope of substrates.
- Yu, Chun-Jiao,Li, Rui,Gu, Peiming
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supporting information
p. 3568 - 3570
(2016/07/18)
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- Palladium-catalyzed fluoride-free cross-coupling of intramolecularly activated alkenylsilanes and alkenylgermanes: Synthesis of tamoxifen as a synthetic application
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We have demonstrated that intramolecular hypercoordination of a carboxylic acid is a powerful activation strategy for the palladium-catalyzed cross-coupling reaction of trialkyl(vinyl)silanes and trialkyl(vinyl)germanes under fluoride-free conditions. Z-β-Trialkylsilyl- and Z-β- trialkylgermylacrylic acids, synthesized stereoselectively by olefination with ynolates, are highly stable and useful reagents for cross-coupling with a variety of aryl iodides to provide tetrasubstituted olefins possessing different carbon substituents in a stereocontrolled and diversity-oriented manner. An application to a stereoselective synthesis of (Z)-tamoxifen is also reported. Copyright
- Matsumoto, Kenji,Shindo, Mitsuru
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supporting information; experimental part
p. 642 - 650
(2012/05/04)
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- Palladium-catalyzed carbonylative coupling reactions of aryl iodides with hexamethyldisilane (HMDS) to benzoyl silanes
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A novel procedure for the palladium-catalyzed carbonylative synthesis of acyl silanes has been developed. Starting from aryl iodides and hexamethyldisilane (HMDS) various benzoyl silanes are produced in moderate to good yields.
- Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
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experimental part
p. 582 - 584
(2012/02/02)
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- Photochemically promoted transition metal-free cross-coupling of acylsilanes with organoboronic esters
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Intermolecular carbon-carbon bond formation between acylsilanes and organoboronic esters was achieved by photoirradiation under almost neutral, transition metal-free conditions. In this reaction, siloxycarbenes generated by photoisomerization of acylsilanes reacted with boronic esters to give the formal B-C bond insertion intermediates, which underwent unique rearrangement to afford the cyclic α-alkoxyboronic esters. Acidic treatment of the resulting crude products under air furnished the cross-coupled ketones in good yields.
- Ito, Kazuta,Tamashima, Hiroto,Iwasawa, Nobuharu,Kusama, Hiroyuki
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supporting information; experimental part
p. 3716 - 3719
(2011/05/14)
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- Reversed-polarity synthesis of diaryl ketones via palladium-catalyzed cross-coupling of acylsilanes
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Acylsilanes serve as acyl anion equivalents in a palladium-catalyzed cross-coupling reaction with aryl bromides to give unsymmetrical diaryl ketones. Water plays a unique and crucial activating role in these reactions. High-throughput experimentation techniques provided successful reaction conditions initially involving phosphites as ligands. Ultimately, 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane was identified as giving a longer-lived catalyst with higher turnover numbers. Its use, in conjunction with a palladacycle precatalyst, led to optimal reaction rates and yields. Scope and limitations of this novel method are presented along with initial mechanistic insight.
- Schmink, Jason R.,Krska, Shane W.
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supporting information; scheme or table
p. 19574 - 19577
(2012/01/13)
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- Can relief of ring-strain in a cyclopropylmethyllithium drive the Brook rearrangement?
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α-Cyclopropyl-α-trialkylsilyl alkoxides were formed either by addition of cyclopropyllithiums to acylsilanes or by addition of organolithiums to a cyclopropylformylsilane. [1,2]-Brook rearrangement led to α-silyloxy organolithiums which on warming underwent cyclopropane ring opening and [1,5]-retro-Brook rearrangement to yield γ-silyl ketones. Despite the favourability of the cyclopropane ring opening, the Brook rearrangement still required the presence of an anion stabilising group to proceed. β-Silylketones were similarly formed by Brook-retro-Brook rearrangement on warming acylsilanes with a vinyllithium.
- Clayden, Jonathan,Watson, David W.,Chambers, Mark
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p. 3195 - 3203
(2007/10/03)
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- Facile photochemical synthesis of mixed siloxyacetal glycosides as potential pH-sensitized prodrugs for selective treatment of solid tumors
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Photochemical reactions of a variety of acylsilanes with peracetylated free glycosides in anhydrous benzene at ambient temperature yielded novel, highly acid-sensitive siloxyacetal glycosides in 75-90% yields with complete retention of configuration at the anomeric center. Subsequent deacetylation of triisopropylsiloxy- and tert-butyldimethylsiloxy derivatives with sodium methoxide in methanol afforded deprotected siloxyacetal glycosides in nearly quantitative yields. Acid hydrolysis of trimethylsilyl siloxyacetals proceeded with a half-life of 17.5 minutes at pH 6.2 which is vastly superior to the decomposition rate of conventional acetals under similar conditions. The structure of one of the novel siloxyacetals was confirmed by X-ray crystallography. In vitro biological studies showed that glucose-derived siloxyacetals may serve as potential pH-activated prodrugs for selective treatment of solid tumors.
- Svarovsky, Serge A.,Taraban, Marc B.,Barchi Jr., Joseph J.
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p. 3155 - 3161
(2007/10/03)
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- Optically pure α-(trimethylsilyl)benzyl alcohol: A practical chiral auxiliary for oxocarbenium ion reactions
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(matrix presented) Enantiopure (S)-α-(trimethylsilyl)benzyl alcohol (98% ee) was prepared by Noyori's transfer hydrogenation of benzoyltrimethylsilane. The corresponding trimethylsilyl ether was subjected to Marko's silyl modified Sakurai conditions with
- Cossrow, Jennifer,Rychnovsky, Scott D.
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p. 147 - 150
(2007/10/03)
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- A simple method for mild oxidation of α-hydroxysilanes to provide aroylsilanes
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Potassium permanganate supported onto alumina in hexane-water is a good oxidizing agent to convert α-hydroxysilanes into acylsilanes. This mild oxidation afforded aroylsilanes having electron-donating groups attached to the aromatic ring, in 70-86% yield.
- Patrocinio,Moran
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p. 2457 - 2461
(2007/10/03)
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- Synthesis of acylsilanes via oxidative hydrolysis of 2-silyl-1,3-dithianes mediated by N-bromosuccinimide
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The oxidative method for the hydrolysis of 1,3-dithianes was applied to 2-silyl-1,3-dithianes using N-bromosuccinimide providing acylsilanes with good yields under a short reaction period. The oxidation of aroylsilanes to carboxylic acid was prevented by
- Patrocínio, Amauri F.,Moran, Paulo J.S.
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p. 220 - 224
(2007/10/03)
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- One-pot preparation of aroylsilanes by reductive silylation of methyl benzoates
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A one-pot synthesis of aroylsilanes based on reductive silylation of methyl benzoates using Mg/I2/chlorosilane in nontoxic 1-methyl-2- pyrrolidinone (NMP) solvent, is described. The yields are moderate to good and the method has been used for the preparation of some new bifunctional aroylsilanes.
- Tongco, Emily C.,Wang, Qunjie,Prakash, G.K. Surya
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p. 2117 - 2123
(2007/10/03)
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- Reductions, reductive alkylations, and intramolecular cyclizations of acyl silanes with samarium diiodide or tributyltin hydride
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A series of acyl silanes including aliphatic-, aromatic-, and bis-acyl silanes, as well as the acyl silanes bearing other substituents such as a bromine atom and alkenyl, succinimide, and carbonyl groups, were prepared, and their reactions with samarium diiodide or tributylstannane were studied. The reactions of acyl silanes occurred in various manners such as reductions, reductive alkylations, intramolecular radical cyclizations, pinacol couplings, aldol reactions, and Tishchenko reactions, depending on the nature of substrates and reaction conditions. Acyl silanes were generally reduced to give the corresponding α-silyl alcohols without transfer of silyl groups. Intramolecular radical cyclizations of 5-hexenoyl silanes and 1-silyl-1,5-pentanedione were realized to give α-silyl cyclopentanols and 1,2-cyclopentanediol derivatives, respectively. On treatment with samarium diiodide in tetrahydrofuran, 1-(trimethylsilyl)-1,6-hexanedione underwent a pinacol coupling reaction in the presence of t-BuOH, whereas it underwent a Tishchenko reaction in the presence of MeOH. The Tishchenko reaction of 1-silyl-1,5-pentanedione gave a δ-silyl-δ-lactone. On treating with samarium diiodide, 1-(trimethylsilyl)-1,5-hexanedione and 1,5-bis(trimethylsilyl)-1,6-hexanedione, underwent, respectively, intramolecular aldol reactions.
- Chuang, Tsung-Hsun,Fang, Jim-Min,Jiaang, Weir-Torn,Tsai, Yeun-Min
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p. 1794 - 1805
(2007/10/03)
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- A novel synthesis of acylsilanes
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A mild and general preparative method for acylsilane is presented. This novel method can be applied without any difficulty to α-chiral, α-alkoxy and multifunctionalized compounds.
- Nakada, Masahisa,Nakamura, Sei-Ichi,Kobayashi, Susumu,Ohno, Masaji
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p. 4929 - 4932
(2007/10/02)
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- Reactions of Acyl Silanes with Fluoride Ion
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Acyl silanes react with fluoride ion to give products arising either from intermediates equivalent to acyl anions or from rearrangement involving alkyl group migration from the silicon atom to the carbonyl carbon atom, depending upon acyl silane structure and reaction conditions.
- Page, Philip C. Bulman,Rosenthal, Stephen
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p. 2351 - 2363
(2007/10/02)
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- Silylative Decarbonylation: A New Route to Arylsilanes
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A new synthetic procedure for the preparation of aromatic chlorosilanes via the palladium-catalyzed reaction of methylchlorodisilanes and aromatic acid chloride is described.The silylative decarbonylation process is solventless, can utilize low metal catalyst loadings (500-1000 ppm Pd), is carried out under moderate conditions (145 deg C), and selectively gives aromatic chlorosilanes in good yield, generally 60-85percent.The procedure is tolerant of a variety of aromatic substituents, for example, alkyl, halo, nitro, cyano, imide, acid anhydride, etc., and the synthesis ofseveral new substituted aromatic chlorosilanes containing benzoyl chloride and phthalic anhydride moieties is described.Chloromethyldisilane starting reagents are available from the direct reaction of methyl chloride and silicon, making this methodology an attractive synthetic route to functionalized aromatic chlorosilanes.
- Rich, Jonathan D.
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p. 5886 - 5893
(2007/10/02)
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- Preparation of substituted benzoyltrimethylsilanes and -germanes by the reaction of benzoyl chlorides with hexamethyldisilane or -digermane in the presence of palladium complexes as catalysts
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Benzoyltrimethylsilanes are prepared in moderate to good yields (24-81%) from the novel reaction of hexamethyldisilane with benzoyl chlorides, catalyzed by dichloro(η3-allyl)dipalladium(II) (1) and triethyl phosphite. The reaction tolerates a wide variety of meta and para substituents on the phenyl ring. Hexamethyldigermane and several bimetallic silicon-germaniums were also used in the reaction; the relative rates of group transfer from competitive benzoylation reactions are PhMe2Ge > Me3Ge > PhMe2Si > Me3Si. Ortho-substituted benzoyl chlorides and aliphatic acid chlorides gave lower yields of the corresponding acyltrimethylsilanes under the same reaction conditions.
- Yamamoto, Keiji,Hayashi, Atsushi,Suzuki, Shigeaki,Tsuji, Jiro
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p. 974 - 979
(2008/10/08)
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- CONVENIENT PREPARATION OF ACYLTRIMETHYLSILANES FROM CARBOXYLIC ACID DERIVATES
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Acylsilanes are prepared in good yields by the reaction of acid chlorides (or anhydrides) with LiAl(SiMe3)4 or LiMeAl(SiMe3)3 in the presence of a catalitic amount of CuCN.
- Kang, Jahyo,Lee, Jae Hyoung,Kim, Koan Seong,Jeong, Jae Uk,Pyun, Chongsuh
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p. 3261 - 3262
(2007/10/02)
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- Dye-Sensitized Photooxidation of Silyl Diazo Compounds. Intramolecular Oxygen Transfer of Carbonyl Oxides
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The dye-sensitized photooxidation of silyl diazo compounds produced the corresponding silyl ketones and silyl esters, and the latter may be formed by the rearrangement of silyl-substituted carbonyl oxides.The reactions of a carbonyl oxide with various silyl ketones were also studied.The dye-sensitized photooxidation of diphenyldiazomethane in the presence of silyl ketones gave silyl esters together with benzophenone by reactions of a carbonyl oxide with the silyl ketones accompanying 1,2-anionic rearrangement of the silyl group.
- Sekiguchi, Akira,Kabe, Yoshio,Ando, Wataru
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p. 2900 - 2903
(2007/10/02)
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- PREPARATION OF SUBSTITUTED BENZOYLTRIMETHYLSILANES BY THE PALLADIUM-CATALYZED SILYLATION OF SUBSTITUTED BENZOYL CHLORIDES WITH HEXAMETHYLDISILANE
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A direct preparative route to benzoyltrimethylsilane has been found by the reaction of benzoyl chloride with hexamethyldisilane in the presence of a specified palladium(II) complex as catalyst.
- Yamamoto, Keiji,Suzuki, Shigeaki,Tsuji, Jiro
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p. 1653 - 1656
(2007/10/02)
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- THE CONVERSION OF α,α-DIBROMOBENZYLSILANES INTO ACYLSILANES ON SILICA GEL
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Acylsilanes may be prepared in high yield by treating α,α-dibromobenzylsilanes with silica gel
- Degl'Innocenti, Alessandro,Walton,David R. M.,Seconi, Giancarlo,Pirazzini, Graziella,Ricci, Alfredo
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p. 3927 - 3928
(2007/10/02)
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