- 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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- 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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- Zinc-Catalyzed Synthesis of Acylsilanes Using Carboxylic Acids and a Silylborane in the Presence of Pivalic Anhydride
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Zinc-catalyzed synthesis of acylsilanes using carboxylic acids and a silylborane has been achieved in the presence of pivalic anhydride. Various carboxylic acids were converted to the corresponding acylsilanes. The in situ formation of mixed anhydrides wa
- Tatsumi, Kenta,Tanabe, Sae,Tsuji, Yasushi,Fujihara, Tetsuaki
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p. 10130 - 10133
(2019/12/24)
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- Tertiary α-Silyl Alcohols by Diastereoselective Coupling of 1,3-Dienes and Acylsilanes Initiated by Enantioselective Copper-Catalyzed Borylation
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An efficient synthesis of functionalized tertiary α-silyl alcohols by an enantio- and diastereoselective copper-catalyzed three-component coupling of 1,3-dienes, bis(pinacolato)diboron, and acylsilanes is reported. The reaction proceeds well with different 1,3-dienes and a broad range of aryl- as well as alkenyl- but also alkyl-substituted acylsilanes. The target compounds are formed with high regio-, diastereo-, and enantioselectivity (up to 99 % ee and d.r. >20:1) and are highly versatile synthetic building blocks.
- Feng, Jian-Jun,Oestreich, Martin
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p. 8211 - 8215
(2019/05/27)
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- Nickel-Catalyzed Synthesis of Silanes from Silyl Ketones
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An unprecedented nickel-catalyzed decarbonylative silylation via CO extrusion intramolecular recombination fragment coupling of unstrained and nondirecting group-Assisted silyl ketones is described. The inexpensive and readily available catalyst performs
- Srimontree, Watchara,Lakornwong, Waranya,Rueping, Magnus
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supporting information
p. 9330 - 9333
(2019/11/19)
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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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p. 2585 - 2589
(2017/08/16)
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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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- Synthesis of acylsilanes by copper(I)-catalyzed addition of silicon nucleophiles onto acid derivatives
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The transition metal-catalyzed transfer of silicon nucleophiles onto various electrophiles has recently gained considerable attention, due to the now readily available silicon pro-nucleophiles such as silylboronates. Our interest lies in the addition of such species to acid derivatives for the generation of acylsilanes. We report herein an efficient method to synthesize these compounds, starting from easy-to-form anhydrides, with very good yields. Copyright
- Cirriez, Virginie,Rasson, Corentin,Riant, Olivier
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p. 3137 - 3140
(2013/12/04)
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- Efficient synthesis of α-tertiary α-silylamines from aryl sulfonylimidates via one-pot, sequential C-Si/C-C bond formations
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An efficient and flexible route for the synthesis of α-tertiary (α,α-dibranched) α-silylamines via sequential reactions of sulfonylimidates using readily available phenyldimethylsilyllithium and Grignard reagents is described. The procedure allows successive formation of C-Si/C-C bonds in a single flask.
- Han, Xiao-Jun,Yao, Ming,Lu, Chong-Dao
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p. 2906 - 2909
(2012/07/14)
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- Synthesis of acylsilanes by palladium-catalyzed cross-coupling reaction of thiol esters and silylzinc chlorides
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An acylsilane synthesis by a Pd-catalyzed cross-coupling reaction of thiol esters and silylzinc chlorides was developed. S-Phenyl thiol esters with a variety of functional groups were converted to corresponding acylsilanes.
- Azuma, Hiroki,Okano, Kentaro,Tokuyama, Hidetoshi
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p. 959 - 961
(2011/12/05)
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- Chiral silanes via asymmetric hydrosilylation with catalytic CuH
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CuH-catalyzed asymmetric conjugate reduction of β-silyl-α, β-unsaturated esters has been developed. Using PMHS as a stoichiometric source of hydride and in situ generated CuH ligated by Solvias' JOSIPHOS analogue PPF-P(t-Bu)2 leads to highly enantioselective 1,4-reductions.
- Lipshutz, Bruce H.,Tanaka, Naoki,Taft, Benjamin R.,Lee, Ching-Tien
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p. 1963 - 1966
(2007/10/03)
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- Oxidation of gem-borylsilylalkylcoppers to acylsilanes with air
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1-Boryl-1-silylalkylcoppers react with molecular oxygen in the presence of pyridine to afford acylsilanes efficiently. The one-pot process consists of two reactions: alkylation of 1-boryl-1-chloro-silylmethyllithium with Grignard reagents in the presence of copper(I) cyanide and aerobic oxidation of the alkylcopper species. This procedure enables us to access the divergent synthesis of acylsilanes.
- Kondo, Junichi,Shinokubo, Hiroshi,Oshima, Koichiro
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p. 1185 - 1187
(2007/10/03)
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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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- Synthesis of Optically Pure Arylsilylcarbinols and Their Use as Chiral Auxiliaries in Oxacarbenium Ion Reactions
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A family of arylsilylcarbinols was synthesized and investigated as chiral auxiliaries for oxacarbenium ion reactions. The optically pure arylsilylcarbinols were prepared using Noyori's transfer hydrogenation catalyst 11. The transfer hydrogenation shows very good enantioselectivities and turnover efficiency for the aryl silyl ketones and is the method of choice for preparing these optically pure alcohols. The diastereoselective addition of allyltrimethylsilane to an in situ generated oxacarbenium ion was explored using Marko's conditions. The selectivity for a representative aliphatic aldehyde was very good, but the selectivity was significantly reduced with unsaturated and aromatic aldehydes. The range of selectivities with different auxiliaries was narrow, and the most practical auxiliary is the phenylsilylcarbinol 2.
- Huckins, John R.,Rychnovsky, Scott D.
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p. 10135 - 10145
(2007/10/03)
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- Synthesis of Acylsilanes from Amides and Esters, and the Selective Oxidation of α-Silyl Alcohols to Aldehydes
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The acylsilanes 2 can easily be made directly from the dimethylamides 3 by treatment with phenyldimethylsilyllithium.They can also be made in two steps from the esters 4 using 2 equiv. of phenyldimethylsilyllithium followed by oxidation of the disilyl alcohols 5 with PDC.The disilyl alcohols 5 can be used as intermediates in the conversion of esters into aldehydes without recourse to hydride reagents, by monodesilylation, using a Brook rearrangement, followed by oxidation and selective removal of the silyl group, using chromium trioxide in DMSO.
- Fleming, Ian,Ghosh, Usha
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p. 257 - 262
(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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- THE SILYL-CUPRATION AND STANNYL-CUPRATION OF ALLENES
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The stoichiometric silyl-cupration of allene 7, followed directly by treating the intermediate cuprate with a proton, with a range of carbon electrophiles, and with chlorine gives the vinylsilanes 8-13.Alternatively, when iodine is the electrophile, the product is the vinyl iodide 16.This can then be metallated and treated with a proton or a range of carbon electrophiles to give the allylsilanes 18-21.More-substituted allenes also undergo silyl-cupration followed by protonation, phenylallenes giving vinylsilanes, and alkylallenes giving, on the whole, allylsilanes.Stoichiometric stannyl-cupration of allenes takes place, with similar but less reliable regiocontrol to that of the corresponding silyl-cupration.
- Fleming, Ian,Rowley, Michael,Cuadrado, Purificacion,Gonzalez-Nogal, Ana M.,Pulido, Francisco J.
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p. 413 - 424
(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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- 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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