- Synthesis of Chiral α-Aminosilanes through Palladium-Catalyzed Asymmetric Hydrogenation of Silylimines
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The asymmetric hydrogenation of silylimines was first developed by using a palladium complex of a P-stereogenic diphosphine ligand as the catalyst, affording the valuable chiral α-aminosilanes with quantitative conversions and excellent enantioselectiviti
- Fan, Dongyang,Liu, Yang,Jia, Jia,Zhang, Zhenfeng,Liu, Yangang,Zhang, Wanbin
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supporting information
p. 1042 - 1045
(2019/05/16)
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- Enantio-, Regio- and Chemoselective Copper-Catalyzed 1,2-Hydroborylation of Acylsilanes
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Enantioselective synthesis of synthetically significant (α-hydroxyallyl)silanes, (α-hydroxyaryl)silanes, and (α-hydroxyalkyl)silanes is reported. The present copper-catalyzed 1,2-selective hydroborylation of acylsilanes affords the aforementioned products
- Nagy, Audric,Collard, Laurent,Indukuri, Kiran,Leyssens, Tom,Riant, Olivier
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supporting information
p. 8705 - 8708
(2019/06/13)
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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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- Lewis Acid-Assisted Photoinduced Intermolecular Coupling between Acylsilanes and Aldehydes: A Formal Cross Benzoin-Type Condensation
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Intermolecular carbon–carbon bond-forming reaction between readily available acylsilanes and aldehydes was achieved under photoirradiation conditions with assistance of a catalytic amount of Lewis acid. Nucleophilic addition of photochemically generated s
- Ishida, Kento,Tobita, Fumiya,Kusama, Hiroyuki
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supporting information
p. 543 - 546
(2017/12/07)
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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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- 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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- Metal-free relay oxidation: Valuable synthesis of acylsilane and ketones under aerobic oxidation
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In this letter, an example of interesting metal-free relay air oxidation of -hydroxysilanes, promoted by the hydroperoxidated carbonyl compounds derived from the Michael reaction of 5,5-dimethylcyclohexane-1,3-dione and chalcone, is reported. A series of aromatic acylsilanes with TBDPS were obtained in promising isolated yields. In addition, as an extension of the relay oxidation under aerobic conditions, this catalyst-free relay oxidation induced by diketone can be applied to the oxidation of general aromatic alcohols (up to 75% yield). Georg Thieme Verlag Stuttgart · New York.
- Bai, Xing-Feng,Gao, Guang,Zheng, Zhan-Jiang,Li, Fei,Lai, Guo-Qiao,Jiang, Kezhi,Li, Fuwei,Xu, Li-Wen
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p. 3031 - 3035
(2012/01/05)
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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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- 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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- 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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- Tandem carbon-carbon bond constructions via catalyzed cyanation/Brook rearrangement/C-acylation reactions of acylsilanes
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(equation presented) A tandem nucleophile-catalyzed cyanation/Brook rearrangement/C-acylation has been developed. Phase transfer cocatalysts facilitate cyanide-catalyzed reactions between acylsilanes and cyanoformates to afford protected tertiary carbinol
- Linghu, Xin,Nicewicz, David A.,Johnson, Jeffrey S.
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p. 2957 - 2960
(2007/10/03)
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- Imidoylstannanes, Improved Preparation and Uses as Acylanion Equivalents
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An improved preparation of imidoylstannanes, by reaction of triorganostannyllithiums with imidoyl chlorides, is reported.This reaction is effective when phenyl or methyl groups are substituents on the tin atom, and when N-aryl C-alkyl or C-aryl imidoyl chlorides are used.After reaction with acyl chlorides, imidoylstannanes led to high yields of α-keto imines, which can be further hydrolysed into α-diketones.Transmetallation with organolithiums selectively gave the corresponding lithium reagents which showed a normal behaviour with alkyl halides, silicon halides, epoxides or chloroformates, leading to functional imines, hydrolysable to the corresponding ketones.This route forms a new entry to Walborski reagents.
- Jousseaume, Bernard,Vilcot, Nathalie,Ricci, Alfredo,Tiekink, Edward R. T.
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p. 2283 - 2288
(2007/10/02)
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- Mixed organofluorine-organosilicon chemistry; 2. Synthesis of alkyl and aryl perfluoroalkyl trialkylsilyl carbinols
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1-Alkyl- and 1-aryl-1-trialkylsilyl-1-perfluoroalkanols, a new class of alcohols, were synthesized from acyl or aroylsilanes and perfluoroorganomagnesium reagents, and their spectroscopic characteristics are described.
- Dondy,Doussot,Portella
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p. 995 - 998
(2007/10/02)
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