1130-17-2Relevant academic research and scientific papers
29Si-1H IMPACT HMBC: A suitable tool for analyzing silylated derivatives
Farjon, Jonathan,Giros, Audrey,Deloisy, Sandrine,Blanco, Luis,Hannedouche, Jerome,Schulz, Emmanuelle,Merlet, Denis
, p. 230 - 233 (2013)
A modified version of the IMPACT heteronuclear multiple bond correlation (HMBC) has allowed the characterization of an organosilane and a tetrasilylated yttrium complex. With the help of this sequence, an average gain in sensitivity close to 2 has been ob
Me3Si?SiMe2[oCON(iPr)2?C6H4]: An Unsymmetrical Disilane Reagent for Regio- and Stereoselective Bis-Silylation of Alkynes
Xiao, Peihong,Cao, Yanjun,Gui, Yingying,Gao, Lu,Song, Zhenlei
, p. 4769 - 4773 (2018)
The air-stable unsymmetrical disilane Me3Si?SiMe2[oCON(iPr)2C6H4] has been developed for bis-silylation of alkynes. This reagent tolerates a range of functional groups, providing Z-vinyl disilanes in
Boron-metal exchange reaction of silylboranes with organometallic reagents: A new route to arylsilyl anions
Kawachi, Atsushi,Minamimoto, Takashi,Tamao, Kohei
, p. 1216 - 1217 (2001)
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.
METHOD FOR PRODUCING SILYL SODIUM COMPOUND AND METHOD FOR DEOXIDIZING EPOXY COMPOUND
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Paragraph 0090-0092, (2020/05/06)
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
Rhodium-Catalyzed Intermolecular trans-Disilylation of Alkynones with Unactivated Disilanes
He, Tao,Liu, Li-Chuan,Guo, Le,Li, Bin,Zhang, Qing-Wei,He, Wei
supporting information, p. 10868 - 10872 (2018/07/31)
Disilylation of alkynes could provide rapid entry to synthetically useful 1,2-bissilyl-alkenes, but is currently limited to activated disilanes reacting in an intramolecular fashion. Reported herein is an efficient rhodium(I)-catalyzed intermolecular disi
On the reactivity of silylboranes toward lewis bases: Heterolytic B-Si cleavage vs. adduct formation
Kleeberg, Christian,Borner, Corinna
supporting information, p. 2799 - 2806 (2013/07/11)
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
Facile synthesis of hypersilylated aromatic compounds by palladium-mediated arylation reaction
Lesbani, Aldes,Kondo, Hitoshi,Sato, Jun-Ichi,Yamanoi, Yoshinori,Nishihara, Hiroshi
scheme or table, p. 7784 - 7786 (2010/12/19)
The treatment of aryl iodides with tris(trimethylsilyl)silane in the presence of Pd(P(tBu)3)2 and the Huenig base leads to the formation of hypersilylated aromatic products in good to excellent yields without cleavage of weak Si-Si b
The preparation and analysis of the phenyldimethylsilyllithium reagent and its reaction with silyl enol ethers
Fleming, Ian,Roberts, Richard S.,Smith, Stephen C.
, p. 1209 - 1214 (2007/10/03)
Phenyldimethylsilyllithium is formed from lithium and phenyldimethylsilyl chloride by slow cleavage of the Si-Si bond of 1,1,2,2-tetramethyl-1,2-diphenyldisilane after the rapid formation of the disilane. 1,1,2,2-Tetramethyl-1,2-diphenyldisiloxane, produced from the silyl chloride by reaction with oxides and hydroxides on the lithium metal surface, is cleaved by dimethyl(phenyl)silyllithium to give lithium dimethyl(phenyl)silanoxide. Dimethyl(phenyl)silyllithium reacts with 1,2-dibromoethane to give dimethyl(phenyl)silyl bromide, which is so rapidly consumed by excess silyllithium reagent that it does not interfere with the double titration used to measure its concentration. Dimethyl(phenyl)silane, produced by protonation of the silyllithium reagent, is also consumed by the silyllithium reagent to give 1,1,2,2-tetramethyl-1,2-diphenyldisilane, which regenerates the silyllithium reagent, as long as lithium is still present. By-products in the preparation of dimethyl(phenyl)silyllithium include 1,3-diphenyl-1,1,2,2,3,3-hexamethyltrisilane, dimethyldiphenylsilane and 1,4-bis[dimethyl(phenyl)-silyl]benzene. Dimethyl(phenyl)silyllithium displaces the silyl group from the tert-butyldimethylsilyl enol ether of cyclohexanone to give the lithium enolate under relatively mild conditions.
Kinetic Control in the Cleavage of Unsymmetrical Disilanes
Hevesi, Laszlo,Dehon, Michael,Crutzen, Raphael,Lazarescu-Grigore, Adriana
, p. 2011 - 2017 (2007/10/03)
A series of 12 phenyl-substituted arylpentamethyldisilanes 1a-1 have been synthesized in order to examine the regioselectivity of their nucleophilic Si,Si bond cleavage reactions under Still's conditions (MeLi/HMPA/0°C). It has been found that the sensitivity of these reactions to the electronic effects of the substituents in the phenyl ring could be described by the Hammett-type equation log(kA/kB) = 0.4334 + 2.421(Σσ); (correlation coefficient R = 0.983). The kA/kB ratio represents the relative rate of attack at silicon atom A (linked to the aryl ring) or at silicon atom B (away from the aryl ring) of the unsymmetrical disilanes. Thus, the present investigation shows that the earlier belief according to which the nucleophilic cleavage of unsymmetrical disilanes always produces the more stable silyl anionic species (thermodynamic control) should be abandoned, or at least seriously amended: kinetic factors appear to exert a primary influence on the regioselectivity of such reactions. Since the two major kinetic factors (i.e., electrophilic character of and steric hindrance at a given silicon atom) have opposite effects on the orientation of the reaction, it may happen that kinetic and thermodynamic control lead to the same result. For some of the unsymmetrical disilanes studied, the major reaction path was not the Si,Si bond cleavage; instead, Si-aryl bond breaking occurred, producing the corresponding aryl anions.
DARSTELLUNG UND REAKTIVITAET VON PHENYLTHIOSUBSTITUIERTEN OLIGOSILANEN
Uhlig, F.,Stadelmann, B.,Zechmann, A.,Lassacher, P.,Stueger, H.,Hengge, E.
, p. 29 - 40 (2007/10/02)
Phenylthio substituted oligosilanes are obtained from the reaction of oligomeric silicon halides with alkali metal thiophenolates MISPh (MI = Li, Na, K).Si-Si bonds are formed when phenylthiooligosilanes are reacted with alkali metal silicon compounds.Alkali metal thiophenolates, the second reaction products can be separated easily.Quite similarly, Fe-Si bonds are obtained from phenylthiosilanes and Na.In contrast to the related alkali metal halide elimination reactions of organohalooligosilanes, transmetallations are never observed in the thiophenolate reactions.Key words: Monomeric and oligomeric silylthiophenolates, oligomeric silanes with hydrogen, methyl and phenyl substituents; 1H, 13C, 29Si NMR, mass spectroscopy.
