- 1-(Trimethylsilyl)vinyl MIDA Boronate: A Trifunctional C 2 Building Block
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1-(Trimethylsilyl)vinyl MIDA boronate - a trifunctional C 2 building block - is prepared in only two laboratory steps and 54% overall yield starting from readily available trimethyl(vinyl)silane. The title compound undergoes orthogonal functionalization at either of the groups present in its structure, for example, iodination at the trimethylsilyl moiety, epoxidation at the double bond, and Suzuki-Miyaura coupling at the MIDA boronate.
- Ivon, Yevhen M.,Voitenko, Zoya V.,Grygorenko, Oleksandr O.
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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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- Styrylsilane coupling reagents for immobilization of organic functional groups on silica and glass surfaces
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Styrylsilanes serve as new coupling reagents for introducing organic functional groups on silica and glass surfaces. Functionalized styrylsilanes, which are readily prepared via catalytic hydrosilylation of the corresponding phenylacetylenes with silanes, are immobilized on silica through acid catalyzed processes under mild conditions.
- Kim, Soo-Bin,Lee, Chang-Hee,Jun, Chul-Ho
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supporting information
p. 9961 - 9964
(2018/09/10)
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- Preparation of Optically Active cis-Cyclopropane Carboxylates: Cyclopropanation of α-Silyl Stryenes with Aryldiazoacetates and Desilylation of the Resulting Silyl Cyclopropanes
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Optically active cis-cyclopropane carboxylates are prepared via the Rh2(S-PTAD)4-catalyzed cyclopropanation of α-silyl styrenes with aryl diazoacetates followed by desilylation of the resulting silyl cyclopropane carboxylates. The co
- Su, Yan,Li, Qing-Fang,Zhao, Yu-Ming,Gu, Peiming
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supporting information
p. 4356 - 4359
(2016/11/13)
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- Mg-promoted reductive coupling of aromatic carbonyl compounds with trimethylsilyl chloride and bis(chlorodimethylsilyl) compounds
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Mg-promoted reductive coupling of aromatic carbonyl compounds (1) with chlorosilanes, such as trimethylsilyl chloride (TMSCl:2), 1,2- bis(chlorodimethylsilyl)ethane (3) and 1,5-dichlorohexamethyltrisiloxane (4), in N,N-dimethylformamide (DMF) at room temperature brought about selective and facile reductive formation of both of carbon-silicon and oxygen-silicon bonds to give the corresponding α-trimethylsilylalkyl trimethylsilyl ethers (5) and cyclic siloxanes (6), (7) in moderate to good yields, respectively. The present facile and selective coupling may be initiated through electron transfer from Mg metal to aromatic carbonyl compounds (1).
- Uchida, Tetsuro,Kita, Yoshio,Maekawa, Hirofumi,Nishiguchi, Ikuzo
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p. 3103 - 3111
(2007/10/03)
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- A new silicon-mediated elimination-rearrangement
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Treatment of trimethylsilylethanes bearing α-phenyl groups and β-phenylthio, phenylsulfonyl or cyano groups with LDA causes elimination-rearrangement mediated by the β-carbanionic species. Mechanistic conclusions are based on isotopic labelling experiment
- Menichetti, Stefano,Stirling, Charles J. M.
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p. 1511 - 1515
(2007/10/03)
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- Mg-promoted reductive cross coupling of carbonyl compounds with trimethylsilyl chloride
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Mg-promoted cross-coupling of aromatic carbonyl compounds with trimethylsilyl chloride (TMSCl) in DMF at room temperature brought about reductive carbon-silicon bond formation to give the corresponding α-trimethylsilylalkyl trimethylsilyl ethers selectively in good yields.The reaction may be initiated through electron transfer from Mg metal to the carbonyl compounds.
- Ishino, Yoshi,Maekawa, Hirofumi,Takeuchi, Hiroshi,Sukata, Kazuaki,Nishiguchi, Ikuzo
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p. 829 - 830
(2007/10/03)
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- Selective formation of alkenes from trimethylsilylmethyl ketones and from acylsilanes
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Trimethylsilylmethyl ketones, readily available from acyl chlorides, undergo a Reformatsky-Peterson reaction sequence to give 3-alkenoates regioselectively.Acylsilanes, however, react with either zinc ester enolates or trimethylsilylmethylmagnesium chloride to give the corresponding tertiary alcohols which, depending on their structure, spontaneously undergo either elimination or a Brook rearrangement-Peterson olefination sequence.These reactions allow the selective formation of vinylsilanes.
- Fuerstner, Alois,Kollegger, Gerlinde,Weidmann, Hans
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p. 295 - 305
(2007/10/02)
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- Synthesis of 3-substituted furans by directed lithiation and palladium catalysed coupling
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The 5-position of the furan ring of 4,4-dimethyl-2-(2-furyl)oxazoline (1a) was protected by a trimethylsityl group. The product, compound (2a), was then lithiated at the 3-position with sec-butyllithium and converted to the bromozinc species (2d) with zinc bromide. Coupling reactions with a range cf aryl-, acyl-, and vinyl halides were performed with Pd(PPh3)4 as catalyst. The reaction with (1-bromoethenyl)- trimethylsilane is abnormal in that it gives a mixture of two products (21) and (2m). The origin of the abnormal product (21) is discussed. The coupling reactions of this silane with 2-thienyl-, 2-furyl-, and phenyl-zinc bromide have also been carried out: in each case, a mixture of the expected coupling product and an isomer, the ethen-2-yltrimethylsilane, was obtained. The ratio of products is shown to depend upon the temperature at which the coupling is carried out. 4,4-Dimethyl-2-(2-thienyl)oxazoline (1b) was lithiated at the 3-position of the thiophene ring and coupled to iodobenzene without protection of the 5-position.
- Ennis, David S.,Gilchrist, Thomas L.
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p. 2623 - 2632
(2007/10/02)
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- Unified synthesis of vinylsilanes and silylated butadienes. Nickel-catalyzed olefination and silylolefination of dithioacetals
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A simple unified reaction has been developed in the syntheses of various vinylsilanes and silylated butadienes by the nickel-catalyzed coupling of dithioacetals with appropriate Grignard reagents. Reactions of 2-aryl-2-(trimethylsilyl)dithianes with MeMgI
- Ni, Zhi-Jie,Yang, Pin-Fan,Ng, Dennis K. P.,Tzeng, Yih-Ling,Luh, Tien-Yau
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p. 9356 - 9364
(2007/10/02)
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- β-SILYL CARBENES
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β-Trimethylsilyl carbenes rearrange to form alkenes by facile migration of the β-silyl group.In the norbornyl system, β-hydrogen migration can also compete with silyl migration.
- Creary, Xavier,Wang, You-Xiong
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p. 2493 - 2496
(2007/10/02)
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- ABNORMAL PRODUCTS OF PALLADIUM CATALYSED REACTIONS OF (1-BROMOVINYL)TRIMETHYLSILANE
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Coupling reactions of (1-bromovinyl)trimethylsilane (1) with organozinc bromides catalyzed by tetrakis(triphenylphosphine)palldium(0) give not only the expected 1-substituted vinylsilanes (2) but also the isomeric 2-substituted vinylsilanes (3).
- Ennis, David S.,Gilchrist, Thomas L.
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p. 3735 - 3736
(2007/10/02)
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- Protophilic versus Silicophilic Reactions in β-Substituted Silanes
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Reactivity in β-eliminations mediated by nucleophilic attack at silicon has been measured as a function of nucleophile, leaving group, and α-substituent; in some instances competition between protophilic and silicophilic reactions is observed.
- Jones, Steven L.,Stirling, Charles J. M.
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p. 1153 - 1154
(2007/10/02)
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- VINYLSILYL GRIGNARD REAGENTS AS ARYNE TRAPS. A NEW ROUTE TO (ARYLALKENYL)SILANES.
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A general method for preparing (arylalkenyl)silanes via nucleophilic capture of arynes with vinyltrimethylsilyl Grignard reagents is decribed.
- Vinod, Thottumkara K.,Hart, Harold
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p. 885 - 888
(2007/10/02)
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- Palladium-Catalyzed Regio- and Stereoselective Aryldesilylation of α-Silylstyrenes with Arenediazonium Salts
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α-Trialkylsilylstyrenes easily reacted with arenediazonium tetrafluoroborates+ BF4- (4)> to give (E)-PhCH=CHAr under palladium(0) catalysis.The bulky substituents on silicon gave better stereoselectivity.
- Ikenaga, Kazutoshi,Matsumoto, Satoshi,Kikukawa, Kiyoshi,Matsuda, Tsutomu
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p. 873 - 876
(2007/10/02)
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- 1H, 13C and 29Si NMR study of α- and β-silylstyrenes and their adducts with dichlorocarbene
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1H, 13C and 29NMR spectra for the α- and β-silylstyrenes (E)-PhCH=CHSiR3 (I) and PhC(SiR3)=CH2 (II) (R = Cl, Me, Ph), and those for some dichlorocarbene adducts of I and II (R = Me, Ph), were examined.From the 13C NMR data, the phenyl substituent in the m
- E. Liepins,Goldberg, Yu.,Iovel, I.,Lukevics, E.
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p. 301 - 312
(2007/10/02)
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- Stereospecific Arylation of Alkenylsilanes with Arylpalladium Acetates
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Alkenyltrimethylsilanes ((E)- and (Z)-RCH=CHSiMe3: R = H, Ph, n-C6H13 and CH3OCH2) stereospecifically reacted at 40 deg C or room temperature with in situ generated phenylpalladium acetate to produce R(Ph)C=CSiMe3 and RCH=C(Ph)SiMe3 with inversion of their geometry.The arylation of CH2=CHSiMe3 with arylpalladium acetates gave (E)-ArCH=CHSiMe3 (Ar = XPH; X = H, 4-Me, 4-MeO, 4-Br, 4-I, 4-EtOCO, and 4-NO2) in good yields.
- Ikenaga, Kazutoshi,Kikukawa, Kiyoshi,Matsuda, Tsutomu
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p. 1276 - 1280
(2007/10/02)
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- REACTION OF DIAZONIUM SALTS WITH TRANSITION METALS IX. REACTION OF VINYLTRIMETHYLSILANE WITH ARENEDIAZONIUM TETRAFLUOROBORATES UNDER PALLADIUM(0) CATALYSIS
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Arenediazonium tetrafluoroborates (ArN2BF4 where Ar = Ph, 4-MeC6H4, 4-BrC6H4, 4-IC6H4 and 4-NO2C6H4) reacted easily with CH2=CHSiMe3 at 25 deg C to give ArCH=CH2, (E)-ArCH=CHSiMe3 and Ar(Me3Si)C=CH2 in excellent yields under palladium(0) catalysis. (E)-ArCH=CHSiMe3 compounds were obtained predominantly and isolated in good yields by using an excess of CH2=CHSiMe3 over ArN2BF4.Protodesilylation of the reaction mixture afforded styrene derivatives.
- Kikukawa, Kiyoshi,Ikenaga, Kazutoshi,Kono, Kiyoshi,Toritani, Koji,Wada, Fumio,Matsuda, Tsutomu
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p. 277 - 282
(2007/10/02)
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