454-57-9Relevant academic research and scientific papers
Reactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions
Nakajima, Yumiko,Tsuchimoto, Takahiro,Chang, Yung-Hung,Takeuchi, Katsuhiko,Ozawa, Fumiyuki
, p. 2079 - 2084 (2016)
Bond activation of silyl compounds, assisted by the cooperative action of non-coordinating anions, is achieved using Cu(i) complexes coordinated with a PNP-pincer type phosphaalkene ligand, [Cu(X)(BPEP-Ph)] (X = PF6 (1a), SbF6 (1b); BPEP-Ph = 2,6-bis[1-phenyl-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine). Complexes 1a and 1b react with Me3SiCN to form Me3SiF and Cu(i) cyanide complexes of the formula [Cu(CN-EF5)(BPEP-Ph)] (E = P (2a), Sb (2b)), in which the CN ligand is associated with the EF5 group arising from EF6-. Formation of the intermediary isonitrile complex [Cu(CNSiMe3)(BPEP-Ph)]+SbF6- (3b) is confirmed by its isolation. Thus, a two-step reaction process involving coordination of Me3SiCN, followed by nucleophilic attack of SbF6- on the silicon atom of 3b is established for the conversion of 1b to 2b. Complex 1b cleaves the H-Si bond of PhMe2SiH as well. The isolation and structural identification of [Cu(BPEP-Ph)]+BArF4- (1c) (BArF4 = B{3,5-(CF3)2C6H3}4) as a rare example of a T-shaped, three-coordinated Cu(i) complex is reported.
Facile synthesis of cyclic fluorosiloxanes
Oguri, Naoki,Takeda, Nobuhiro,Unno, Masafumi
supporting information, p. 1506 - 1508 (2015/11/24)
Novel 1,3,5,7-tetrafluorocyclotetrasiloxanes were synthesized from cyclotetrasiloxanetetraol by a facile synthetic method. By adjusting the amount of the fluorinating reagent, synthesis of a single isomer of 1,3,5,7-tetrafluorocyclotetrasiloxanes as well as the preparation of all four isomers were accomplished. The products are expected to serve as potential precursors to not only well-defined silsesquioxanes but also asymmetric cyclic siloxanes.
Enhanced nucleophilic fluorination and radiofluorination of organosilanes appended with potassium-chelating leaving groups
Al-Huniti, Mohammed H.,Lu, Shuiyu,Pike, Victor W.,Lepore, Salvatore D.
, p. 48 - 52 (2014/01/23)
Here we aimed to explore the feasibility of enhancing the fluorination of organosilanes by appending potassium-chelating groups to the substrates. For this purpose, eight organosilanes were prepared in which a linear or cyclic leaving group, with putative
Zinc-catalyzed nucleophilic substitution reaction of chlorosilanes with organomagnesium reagents
Murakami, Kei,Yorimitsu, Hideki,Oshima, Koichiro
body text, p. 1415 - 1417 (2009/06/28)
Zinc-catalyzed nucleophilic substitution reactions of chlo-rosilanes with organomagnesium reagents afford various tetraorganosilanes under mild reaction conditions. The reactions can be performed on large scale and allow efficient preparation of functionalized tetraorganosilanes.
Selective synthesis of halosilanes from hydrosilanes and utilization for organic synthesis
Kunai, Atsutaka,Ohshita, Joji
, p. 3 - 15 (2007/10/03)
Selective synthesis of halosilanes has been examined. Various types of halosilanes and halohydrosilanes, such as R3SiX, R2SiHX, R2SiX2, RSiH2X, RSiHX2 (X=Cl, Br, F), were obtained by the reactions of the corresponding hydrosilanes with Cu(II)-based reagents selectively in high yields. This method could be also applied to the synthesis of chlorofluorosilanes and chlorohydrogermanes. On the other hand, iodo- and bromosilanes and germanes were obtained by Pd- or Ni-catalyzed hydride-halogen exchange reactions of hydrosilanes with alkyl or allyl halides. Their synthetic applications have been demonstrated by using iodo- and bromosilanes and chlorofluorosilanes.
Tetrabutylammonium butyldifluorodimethylsilicate and difluorodimethylphenylsilicate, new nucleophilic fluorinating reagents
Kví?ala,Mysík,Paleta
, p. 547 - 549 (2007/10/03)
Tetrabutylammonium butyldifluorodimethylsilicate (TAMBS, 1a) and tetrabutylammonium difluorodimethylphenylsilicate (TAMPS, 1b) were conveniently prepared from the corresponding substituted fluorodimethylsilanes and tetrabutylammonium fluoride. Both fluorosilicates 1a, 1b are powerful nucleophilic fluorinating reagents which transform primary or secondary halides, tosylates, or mesylates to the corresponding fluorides in moderate to good yields.
A convenient one-pot synthesis of stannylsilanes
Hummeltenberg, Reinhard,Jurkschat, Klaus,Uhlig, Frank
, p. 255 - 261 (2007/10/03)
Stannylsilanes were synthesized in high yields by reaction of organotinchlorides with organofluorosilanes and magnesium. The fluorosilanes were prepared in good yields and under mild conditions by reaction of the corresponding chlorosilanes with [n-Bu4N][Ph3SnF2]. All products were characterized by 29Si, 119Sn NMR spectroscopy and elemental analysis.
The Phenyldimethylsilyl Group as a Masked Hydroxy Group
Fleming, Ian,Henning, Rolf,Parker, David C.,Plaut, Howard E.,Sanderson, Philip E. J.
, p. 317 - 338 (2007/10/02)
A phenyldimethylsilyl group attached to carbon can be converted into hydroxy group 1->5, with retention of configuration at the migrating carbon, by any of three main methods.The first involves protodesilylation, to remove the phenyl ring from the silicon atom, followed by oxidation of the resulting functionalized silicon atom using peracid or hydrogen peroxide.The second uses mercuric acetate for the same purpose, and can be combined in one pot with the oxidative step using peracetic acid.This method has a variant in which the mercuric ion is combined with palladium(II) acetate, both in less than stoichiometric amounts.The third uses bromine, which can also be used in one pot in conjuction with peracetic acid.In this method, but not in the method based on mercuric acetate, the peracetic acid may be buffered with sodium acetate.The method using bromine as the electrophile for removing the benzene ring has a more agreeable variant in which it is administered in the form of potassium bromide, which is oxidised to bromine by the peracetic acid.The scope and limitations of each of these methods are reported with a range of examples possessing between them many of the common functional groups.Simple benzene rings, alcohols, ethers, esters, amides and nitriles are compatible with all three methods, and ketones do not undergo Baeyer-Villiger reaction under any of the conditions.Amines, however, are oxidised to amine oxides.Ketones may be brominated in the third of the three main species.The absence of acid in the third method makes it especially valuable when the phenyldimethylsilyl group has a neighbouring nucleofugal group such as hydroxy or acetoxy.Carbon-carbon double bonds are incompatible with the methods, except for terminal monosubstituted double bonds, which can survive the conditions used in the first of the three methods.
Preparation of the iodides (Me3Si)2C(SiMe2C6H4Y)(SiMe2I) and some related compounds
Eaborn, Colin,Jones, Karen L.,Lickiss, Paul D.
, p. 35 - 42 (2007/10/02)
The preparations of: (a) the iodides (Me3Si)2C(SiMe2C6H4Y)(SiMe2I) (Y=H, p-OMe, p-Me, p-Cl, m-CF3), via the corresponding hydrides; (b) the compounds (Me3Si)2C(SiMe2Ph)(SiMe2X) with X=F, O2CCF3, OMe, N3, NCS and Cl: and (c) the iodide (p-MeC6H4)3CSiMe2I are described. Key words: Silicon; Iodide; Fluoride; Hydride; Trimethylsilyl
Electrochemical Oxidation of Hydrosilanes. A Synthetic Approach to Halosilanes and Disilanes
Kunai, Atsutaka,Kawakami, Toshihiro,Toyoda, Eiji,Sakurai, Tomohiro,Ishikawa, Mitsuo
, p. 1945 - 1948 (2007/10/02)
Electrolytic oxidation of dimethylphenylsilane (1) in the presence of CuCl2 or CuCl afforded chlorodimethylphenylsilane in high yields (>90percent), while similar electrolysis of 1 in the presence of BF4- ions afforded fluorodimethylphenylsilane in 90percent yield. 1,2-Diphenyltetramethyldisilane was obtained from 1 in 48percent yield by the electrolysis with a Pt-Cu electrode system.A "paired" electrolysis of methyldiphenylsilane on the anode and chloromethyldiphenylsilane on the cathode afforded 1,2-dimethyltetraphenyldisilane in 64percent yield.
