- Zinc Bis(triphenylsilyl) Stabilized by N-Heterocyclic Carbene
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Triphenylsilylzinc compounds stabilized by an N-heterocyclic carbene, [Zn(SiPh3)2(IMes)] (2) and [ZnX(SiPh3)(IMes)] [X = Cl (3a), Br (3b), I (3c)] [IMes = 1,3-Bis(2,4,6-trimethylphenyl)imidazole-2-ylidene], were synthesized by transmetalation from [ZnX2(IMes)(THF)0–1] [X = Cl (1a), Br (1b), I (1c)] and [LiSiPh3(THF)3]. According to single-crystal X-ray diffraction, [Zn(SiPh3)2(IMes)] (2) shows a trigonal-planar coordinated central zinc atom, whereas [ZnCl(SiPh3)(IMes)(THF)] (3a-THF) shows a distorted tetrahedral coordination.
- Lemmerz, Lara E.,Spaniol, Thomas P.,Okuda, Jun
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- METHOD FOR PRODUCING SILYL SODIUM COMPOUND AND METHOD FOR DEOXIDIZING EPOXY COMPOUND
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PROBLEM TO BE SOLVED: To construct a technique which can simply, efficiently and inexpensively synthesize a silyl sodium compound in a small number of processes and in a short time, especially to construct a technique which synthesizes a silyl sodium compound by using easily available reagents from a viewpoint of sustainability without using reagents which are difficult to handle and are toxic. SOLUTION: There is provided a method for synthesizing a silyl sodium compound comprising a step of reacting a dispersion obtained by dispersing a silyl halide compound or a disilane compound with sodium into a dispersion solvent, the silyl halide compound or the disilane compound as a starting compound, in a reaction solvent to obtain the silyl sodium compound. There is also provided a method for deoxidizing an epoxy compound comprising a step of reacting the silyl sodium compound obtained by synthesizing method of the silyl sodium compound with an epoxy compound to deoxidize the epoxy compound to stereoselectively produce an alkene compound. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0087-0089
(2020/05/06)
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- Hydrosilylation catalysis by an earth alkaline metal silyl: Synthesis, characterization, and reactivity of bis(triphenylsilyl)calcium
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Bis(triphenylsilyl)calcium [Ca(SiPh3)2(thf)] obtained in high yield as a crystalline ether adduct catalyzes the hydrosilylation of activated C-C double bonds efficiently and regioselectively. The Royal Society of Chemistry 2014.
- Leich, Valeri,Spaniol, Thomas P.,Maron, Laurent,Okuda, Jun
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supporting information
p. 2311 - 2314
(2014/03/21)
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- On the reactivity of silylboranes toward lewis bases: Heterolytic B-Si cleavage vs. adduct formation
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Silylboranes are important reagents in a variety of catalytic silylation and silaboration reactions. While transition-metal-catalyzed reactions are well established, organo-/Lewis base-catalyzed reactions of silylboranes have only recently emerged. For both catalytic processes the reactivity of silylboranes toward Lewis bases is of relevance. While for organo-catalyzed reactions Lewis base activation of the silylborane has been proposed, transition-metal- and especially copper-catalyzed reactions also frequently require the presence of Lewis basic alkali metal alkoxides. In the present study we explore the reaction of K(18-crown-6) tert-butoxide and the NHC 1,3-diisopropyl-4,5-dimethyl- imidazol-2-ylidene as exemplary Lewis bases with the two silylboranes pinB-SiMe2Ph and pinB-SiPh3 (pin = OCMe 2CMe2O). The reaction with K(18-crown-6) tert-butoxide results in activation of the boron-silicon bond. The isolated product of this activation is either the potassium silyl complex [K(18-crown-6)SiPh3] or [K(18-crown-6)(thf)2][pinB(SiMe2Ph)2], the formal Lewis acid/base adduct of [K(18-crown-6)SiMe2Ph] with pinB-SiMe2Ph. Both complexes react essentially as sources of nucleophilic silyl moieties in reactions with exemplary electrophiles. In contrast, usage of the carbene leads to the formation of isolable Lewis acid/base adducts of the type (NHC)pinB-SiR3, which do not react as sources of nucleophilic silyl moieties. The identification and characterization of these species appears of relevance for the mechanistic understanding and further development of Lewis base/organo- as well as transition-metal-catalyzed silyl transfer reactions. Copyright
- Kleeberg, Christian,Borner, Corinna
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p. 2799 - 2806
(2013/07/11)
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- Boron-metal exchange reaction of silylboranes with organometallic reagents: A new route to arylsilyl anions
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The boron-metal exchange reaction of (arylsilyl)boranes with alkyllithiums, potassium tert-butoxide, and methylmagnesium bromide affords the corresponding silyllithium, silylpotassium, and silylmagnesium compounds, respectively. Especially, the boron-lithium exchange reaction occurs even in hydrocarbon solvents such as toluene and hexane as well as in THF.
- Kawachi, Atsushi,Minamimoto, Takashi,Tamao, Kohei
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p. 1216 - 1217
(2007/10/03)
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- Electroreductive Synthesis of Polysilanes, Polygermanes, and Related Polymers with Magnesium Electrodes
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The electroreduction of alkylaryldichlorosilane carried out with Mg cathode and anode in a single compartment cell gave high molecular weight poly(alkylarylsilane) (Mn = 5200-31000, Mw/Mn = 1.4-1.8) in 5-79% yield. The effects of electrode material, monomer concentration, amount of supplied electricity, and ultrasound were investigated. This electroreductive method was also successfully applied to the synthesis of polygermanes, silane-geramane copolymers, and also poly[p-(disilanylene)phenylenes].
- Kashimura, Shigenori,Ishifune, Manabu,Yamashita, Natsuki,Bu, Hang-Bom,Takebayashi, Masakatsu,Kitajima, Satsuki,Yoshiwara, Daisuke,Kataoka, Yasuki,Nishida, Ryoichi,Kawasaki, Shin-Ichi,Murase, Hiroaki,Shono, Tatsuya
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p. 6615 - 6621
(2007/10/03)
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- Silylenes of the elemental composition C4H2Si: Generation and matrix-spectroscopic identification
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Flash pyrolysis of 1,1-diethynyl-2,2,2-trimethyldisilane (16) and triethynylsilane (18) led to the formation of two silylenes of the elemental composition C4H2Si, namely diethynylsilylene (10) and ethynylsilacyclopropenylidene (7), which were isolated in an argon matrix at 10 K. Both compounds could be photoconverted into another isomer, butadiynylsilylene (9). The identification of these reactive intermediates is based on the comparison between the experimental and calculated IR spectra for the parent compounds as well as for their dideuterated and fully 13C-labeled isotopomers.
- Maier, Guenther,Reisenauer, Hans Peter,Meudt, Andreas
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p. 1285 - 1290
(2007/10/03)
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- Catalytic asymmetric synthesis of β-hydroxy ketones by palladium-catalyzed asymmetric 1,4-disilylation of α,β-unsaturated ketones
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1,4-Disilylation of β,β-unsaturated ketones with 1,1-dichloro-1-phenyl-2,2,2-trimethyldisilane proceeded in the presence of phosphine-palladium catalysts in benzene. High enantio-selectivity (up to 92%) was observed in the disilylation with dichloro[(R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl] palladium(II) as a catalyst (0.5 mol %). The disilylation products, 1-(trimethyisilyloxy)-3-(dichlorophenylsilyl)propenes, were readily converted into optically active α-unsubstituted or anti α-substituted β-(phenyldimethylsilyl) ketones, the oxidation of which gave the corresponding optically active β-hydroxy ketones in high yields.
- Matsumoto, Yonetatsu,Hayashi, Tamio,Ito, Yoshihiko
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p. 335 - 346
(2007/10/02)
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- Efficient formation and cleavage of disilanes by potassium-graphite. Silylation with silyl metal reagents
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Potassium-graphite laminate (C8K) very rapidly forms disilanes from chlorosilanes and then rapidly cleaves the disilanes to give silyl potassium reagents which can be converted into potassium silyl cuprates, -manganates, and -vanadates that are useful for various nucleophilic substitution and addition reactions.
- Fuerstner, Alois,Weidmann, Hans
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- AN ELECTROCHEMICAL METHOD FOR THE SYNTHESIS OF SILICON-SILICON BONDS
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An electrochemical method for the preparation of compounds containing Si-Si bonds has been developed and its scope investigated.
- Hengge, E.,Firgo, H.
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p. 155 - 161
(2007/10/02)
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