79294-25-0Relevant academic research and scientific papers
Synthesis of Alkyl Silanes via Reaction of Unactivated Alkyl Chlorides and Triflates with Silyl Lithium Reagents
Mallick, Shubhadip,Würthwein, Ernst-Ulrich,Studer, Armido
, p. 6568 - 6572 (2020/09/02)
The reaction of unactivated secondary and primary alkyl chlorides as well as primary alkyl triflates with silyl lithium reagents to access tetraorganosilanes is reported. These nucleophilic substitutions proceed in the absence of any transition metal catalyst under mild conditions in moderate to very good yields. The silyl lithium reagents are readily generated from the corresponding commercially available chlorosilanes. Enantioenriched secondary alkyl chlorides react with high stereospecificity under inversion of configuration.
Alkylpotassium-Catalyzed Benzylic C-H Alkylation of Alkylarenes with Alkenes
Sato, Io,Yamashita, Yasuhiro,Kobayashi, Shū
supporting information, p. 240 - 250 (2019/01/04)
Catalytic benzylic C-H alkylation reactions of alkylarenes with alkenes such as β-substituted styrenes and vinylsilanes have been achieved by utilizing alkylpotassium as a catalyst. Various substituted toluene derivatives can be alkylated under mild reaction conditions to afford the desired functionalized hydrocarbons in moderate to high yields.
Air-stable and reusable cobalt ion-doped titanium oxide catalyst for alkene hydrosilylation
Mitsudome, Takato,Fujita, Shu,Sheng, Min,Yamasaki, Jun,Kobayashi, Keita,Yoshida, Tomoko,Maeno, Zen,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
supporting information, p. 4566 - 4570 (2019/08/21)
Alkene hydrosilylation is important for the synthesis of organosilicon compounds, for which precious metal complexes have been used as industrial catalysts. Considering environmental and economic concerns, the development of earth-abundant metal catalysts with high stability, easy separability, and high reusability is strongly desired. Herein, we report that a new cobalt ion-doped titanium dioxide (Co/TiO2) catalyst was synthesized by hydrogen treatment method. The Co/TiO2 catalyst acts as a highly efficient heterogeneous catalyst for the anti-Markovnikov hydrosilylation of alkenes under solvent-free conditions. Various alkenes were selectively converted to the corresponding alkylsilanes. This catalyst showed high stability in air and high reusability with maintained activity. The investigation of the relationship between the active site structure and catalytic performance of Co/TiO2 disclosed that the high stability and durability of Co/TiO2 are originated from the strong interaction between Co and TiO2 through the formation of CoTiO3 solid solution species.
Visible-Light-Mediated Metal-Free Hydrosilylation of Alkenes through Selective Hydrogen Atom Transfer for Si?H Activation
Zhou, Rong,Goh, Yi Yiing,Liu, Haiwang,Tao, Hairong,Li, Lihua,Wu, Jie
supporting information, p. 16621 - 16625 (2017/12/13)
Although there has been significant progress in the development of transition-metal-catalyzed hydrosilylations of alkenes over the past several decades, metal-free hydrosilylation is still rare and highly desirable. Herein, we report a convenient visible-
Regio- and chemoselective silylmetalation of functionalized terminal alkenes
Nakamura, Shinji,Uchiyama, Masanobu
, p. 28 - 29 (2007/10/03)
A regio-/chemoselective silylmetalation of various functionalized alkenes based on the zinc silyl complex in the presence of a catalytic amount of copper cyanide was developed. Silylmetalation of alkenes, followed by electrophilic trapping, proved to be a
Desulfurizative silation, germation, and stannation of thioacetals and their analogues utilizing titanocene(II)
Takeda, Takeshi,Nozaki, Naoki,Fujiwara, Tooru
, p. 3533 - 3536 (2007/10/03)
Desulfurization of thioacetals with the low valent titanium species CP2Ti[P(OEt)3]2 in the presence of trialkylsilanes afforded the corresponding tetraalkylsilanes. Allylsilanes were obtained regioselectively using β,γ-uns
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.
The Phenyldimethylsilyl Group as a Masked Form of the Hydroxy Group
Fleming, Ian,Henning, Rolf,Plaut, Howard
, p. 29 - 31 (2007/10/02)
The phenyldimethylsilyl group can be converted in two steps, protodesilylation and peracid-mediated rearrangement, into a hydroxy group with retention of configuration: β-phenyldimethylsilyl carbonyl compounds are thus revealed to be masked aldol products.
