- Catalytically active, recyclable polymeric titanocene disks: A batch-flow reactor
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Dichlorotitanocene bound within porous polystyrene disks catalyzes the coupling of vinylmagnesium chloride and chlorosilanes to form 1,4-bis(silyl)-2-butenes. A simple batch-flow reactor permits catalyst reuse by repeated addition of fresh reagents and de
- Berget, Patrick E.,Schore, Neil E.
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- Titanocene-mediated homolytic opening of epoxysilanes
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The titanocene(III) chloride mediated opening of silyloxiranes has been examined. Electron transfer from the metal leads to α-silyl radicals with total regiocontrol. The radicals could be trapped by various olefins, and the corresponding adducts were obtained in good yields (Table). Further substitution of the oxirane by alkyl groups proved detrimental to the reactions, but ring opening remained essentially regioselective.
- Puljic, Nicolas,Albert, Matthias,Dhimane, Anne-Lise,Fensterbank, Louis,Lacote, Emmanuel,Malacria, Max
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- New polymers derived from 4-vinylsilylbenzocyclobutene monomer with good thermal stability, excellent film-forming property, and low-dielectric constant
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A series of benzocyclobutene (BCB) polymers derived from a new readily available monomer, 4-(1′,1′-dimethyl-1′-vinyl) silylbenzocyclobutene (4-DMVSBCB), were conveniently prepared by radical and anionic polymerization. The homo- and co-polymerization results show that the reactivity of 4-DMVSBCB in anionic polymerization is relatively higher compared with radical polymerization. The molecular weight of 4-DMVSBCB polymers and content of 4-DMVSBCB can be controlled by anionic copolymerization. The introduction of rigid and crosslinkable BCB building blocks in side chains and carbosilanes in molecule gives rise to insulating materials with good film-forming property, smooth and flat film surface, and low-dielectric constants of 2.41-2.45, as preserving good thermal stability.
- Yang, Junxiao,Liu, Shangchun,Zhu, Fanghua,Huang, Yawen,Li, Bo,Zhang, Lin
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- Platinum Complex-catalysed Dehydrogenative Monosilylation of Alkenes with Disilanes
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Alkenes react with disilanes in the presence of platinum phosphine complex catalysts to give alk-1-enylsilanes.
- Hayashi, Teruyuki,Kawamoto, Aparecida M.,Kobayashi, Toshi-aki,Tanaka, Masato
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- Copper-Catalyzed Asymmetric Hydroallylation of Vinylsilanes
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A copper-catalyzed asymmetric hydroallylation of readily available vinylsilanes with allylic phosphates in the presence of hydrosilane was developed. These transformations can be performed under mild reaction conditions and provide the useful chiral organ
- Guo, Xiaobing,Niu, Junbo,Wang, Simin,Xiong, Tao,Zhang, Qian,Zhang, Qiao
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supporting information
(2022/02/21)
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- Nickel-Catalyzed Reductive Cross-Coupling of Alkyl Bromides and Chlorosilanes
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A novel nickel-catalyzed highly selective reductive cross-coupling of alkyl bromides and chlorosilanes to construct the C-Si bond has been developed. Under benign reaction conditions, a series of structurally interesting organosilanes can be accessed without Ni-catalyzed isomerization. The utility of this chemistry is illustrated by further transformations of the product. Moreover, the radical mechanism of the reaction is illustrated by control experiments.
- Xing, Mimi,Cui, Huanhuan,Zhang, Chun
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supporting information
p. 7645 - 7649
(2021/10/12)
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- Cross-Electrophile C(sp2)?Si Coupling of Vinyl Chlorosilanes
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The cross-electrophile coupling has become a powerful tool for C?C bond formation, but its potential for forging the C?Si bond remains unexplored. Here we report a cross-electrophile Csp2-Si coupling reaction of vinyl/aryl electrophiles with vinyl chlorosilanes. This new protocol offers an approach for facile and precise synthesis of organosilanes with high molecular diversity and complexity from readily available materials. The reaction proceeds under mild and non-basic conditions, demonstrating a high step economy, broad substrate scope, wide functionality tolerance, and easy scalability. The synthetic utility of the method is shown by its efficient accessing of silicon bioisosteres, the design of new BCB-monomers, and studies on the Hiyama cross-coupling of vinylsilane products.
- Duan, Jicheng,Kang, Shaolin,Liu, Xue-Yuan,Qi, Liangliang,Shu, Xing-Zhong,Wang, Ke,Xu, Guang-Li
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supporting information
p. 23083 - 23088
(2020/12/09)
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- Organosilane synthesis method based on alkenyl chlorosilane coupling reaction
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The invention discloses a synthetic method for preparing aryl or alkenyl silane by taking alkenyl chlorosilane as a raw material and carrying out coupling reaction on the alkenyl chlorosilane, an aryland an alkenyl electrophilic reagent. The invention relates to an organosilane synthesis method based on alkenyl chlorosilane coupling reaction. According to the method, alkenyl chlorosilane is usedas a raw material, Mn or Zn is used as a reducing agent under the catalysis of nickel, and the alkenyl chlorosilane and an aryl or alkenyl electrophilic reagent are subjected to a coupling reaction togenerate an R-Si (vinyl) R1R2 type aryl with a structure as shown in a formula II or alkenyl organosilicon compound with a structure as shown in a formula III. According to the invention, the aryl and alkenyl electrophilic reagents are used as substrates to prepare the organosilicon compound with a structure of R-Si (vinyl) R1R2 type, and the method has the advantages of mild reaction conditions,simple and easily available raw materials, wide substrate applicability, good compatibility of reaction functional groups and the like.
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Paragraph 0030-0034
(2020/08/29)
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- Thieme Chemistry Journals Awardees - Where Are They Now? Titanium-Catalyzed Hydroaminoalkylation of Vinylsilanes and a One-Pot Procedure for the Synthesis of 1,4-Benzoazasilines
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Vinylsilanes undergo intermolecular alkene hydroaminoalkylation with secondary amines in the presence of a titanium mono(aminopyridinato) catalyst to give the branched hydroaminoalkylation products with high regioselectivity. Corresponding reactions of a suitable (2-bromophenyl)vinylsilane combined with a subsequent intramolecular Buchwald-Hartwig amination result in the development of an elegant one-pot procedure for the synthesis of 1,4-benzoazasilines.
- Lühning, Lars H.,Rosien, Michael,Doye, Sven
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supporting information
p. 2489 - 2494
(2017/11/04)
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- Hydrosilylation Reaction Catalysts and Curable Compositions and Methods for Their Preparation and Use
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A composition contains (A) a hydrosilylation reaction catalyst and (B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. The composition is capable of reacting via hydrosilylation reaction to form a reaction product, such as a silane, a gum, a gel, a rubber, or a resin. Ingredient (A) contains an iron-organosilicon ligand complex that can be prepared by reacting an iron carbonyl compound and an organosilicon ligand.
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Paragraph 0188; 0189
(2014/10/16)
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- Enantio- and diastereoselective synthesis of syn-β-hydroxyallylsilanes via a chiral (Z)-γ-silylallylboronate
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syn-β-Hydroxyallylsilanes of general structure 11 and 28 are prepared in 50-86% yield and 91-95% ee (for aliphatic aldehydes; 50% ee for benzaldehyde) via the BF3-Et2O-promoted γ-silylallylboration reactions, using reagents 14 and 15.
- Lira, Ricardo,Roush, William R.
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p. 4315 - 4318
(2008/03/11)
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- A concise sultone route to highly oxygenated 1,10-seco-eudesmanolides - enantioselective total synthesis of the antileukemic sesquiterpene lactones (-)-eriolanin and (-)-eriolangin
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Using a sultone as the key intermediate, the first enantioselective total synthesis of the antileukemic 1,10-seco-eudesmanolides (-)-eriolanin (1) and (-)-eriolangin (2) was achieved, which also established the hitherto unknown absolute configuration of t
- Merten, Joern,Hennig, Andre,Schwab, Pia,Froehlich, Roland,Tokalov, Sergey V.,Gutzeit, Herwig O.,Metz, Peter
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p. 1144 - 1161
(2007/10/03)
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- A general synthesis of five, six and seven-membered silasultones via dehydrative cyclisation
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Five, six and seven-membered silasultones can be conveniently prepared in good yield by dehydrative cyclisation of siloxane disulphonic acids. The siloxanes are prepared by protodesilylation of the corresponding phenylsilane sulphonic acids. The sulphonate group is introduced either by free-radical sulphonation of vinyl silanes, or by SN2 sulphite displacement of a long chain alkyl chloride.
- Braddock, D. Christopher,Peyralans, Jér?me J.-P.
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p. 7233 - 7240
(2007/10/03)
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- Rhodium-catalyzed acylation of vinylsilanes with acid anhydrides
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A catalytic acylation of vinylsilane with acid anhydride is accomplished by the use of [RhCl(CO)2]2, in which the transmetalation between vinylsilane and rhodium(I) carbonyl complex plays a key role. The application of this acylation reaction to (1-acyloxyvinyl)silanes provides synthetic methods for α-acyloxy enones, α-diketones, and their derivatives.
- Yamane, Motoki,Uera, Kazuyoshi,Narasaka, Koichi
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p. 477 - 486
(2007/10/03)
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- Formation of 1,4-Disilyl-2-butenes from Vinyl Grignard Reagent and Chlorosilanes Catalyzed by a Titanocene Complex
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(matrix presented) Symmetrical 1,4-disilyl-2-butenes 1 have been prepared by the reaction of vinyl Grignard reagent with chlorosilanes. This reaction proceeds efficiently in the presence of a catalytic amount of titanocene dichloride at 0 °C in THF. When dichlorodiphenylsilane was used, 1,1-diphenyl-1-silacyclo-3-pentene 2 was obtained in a good yield.
- Watabe, Hiroyasu,Terao, Jun,Kambe, Nobuaki
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p. 1733 - 1735
(2007/10/03)
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- Transition Metal Complexes of Troeger's Base and their Catalytic Activity for the Hydrosilylation of Alkynes
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Rhodium(III) and iridium(III) complexes of Troeger's base (TB), of structural type TB*2MCl3 (M=Rh, Ir), were prepared by treatment of TB with MCl3.The rhodium complex readily catalyzed the hydrosilylation of alkynes with high regio- and stereoselectively observed in some cases.
- Goldberg, Yuri,Alper, Howard
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p. 369 - 372
(2007/10/02)
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- The Silylcupration of Acetylenes: a Synthesis of Vinylsilanes
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Bis(dimethylphenylsilyl)copper-lithium (1) reacts with hex-1-yne, propyne, acetylene itself, phenylacetylene, and hex-3-yne to give the products of syn addition of the dimethylphenylsilyl group and the copper.The resultant vinylcopper reagents react with a variety of electrophiles, such as the proton, iodine, acyl and alkyl halides, enones, and epoxides, to give vinylsilanes.With the terminal alkynes, the silyl group becomes attached with a high level of regioselectivity to the terminal carbon atom, with the result that the final products are 2,2-disubstituted vinylsilanes.
- Fleming, Ian,Newton, Trevor W.,Roessler, Felix
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p. 2527 - 2532
(2007/10/02)
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