71864-47-6Relevant articles and documents
A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes
Naganawa, Yuki,Nakajima, Yumiko,Sakamoto, Kei
supporting information, p. 601 - 606 (2021/01/13)
Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si-Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5, and tetrachlorosilane 6 to give the corresponding monochlorosilanes.
Silylarene Hydrogenation: A Strategic Approach that Enables Direct Access to Versatile Silylated Saturated Carbo- and Heterocycles
Wiesenfeldt, Mario P.,Knecht, Tobias,Schlepphorst, Christoph,Glorius, Frank
supporting information, p. 8297 - 8300 (2018/06/29)
We report a method to convert readily available silylated arenes into silylated saturated carbo- and heterocycles by arene hydrogenation. The scope includes alkoxy- and halosilyl substituents. Silyl groups can be derivatized into a plethora of functionalities and find application in organic synthesis, materials science, and pharmaceutical, agrochemical, and fragrance research. However, silylated saturated (hetero-) cycles are difficult to access with current technologies. The yield of the hydrogenation depends on the amount of the silica gel additive. This silica effect also enables a significant improvement of a previously disclosed method for the hydrogenation of highly fluorinated arenes (e.g., to all-cis-C6H6F6).
The synthesis of chlorosilanes from alkoxysilanes, silanols, and hydrosilanes with bulky substituents
Masaoka, Shin,Banno, Tadashi,Ishikawa, Mitsuo
, p. 174 - 181 (2007/10/03)
We have found that commercially important trialkylchlorosilanes can readily be synthesized by the reaction of alkoxysilanes, silanols, and hydrosilanes with aqueous concentrated hydorochloric acid. Treatment of trialkylalkoxysilanes bearing the bulky alkyl substituents, such as the i-Pr, sec-Bu, tert-Bu, and cyclo-Hex group, with 35% aqueous hydrochloric acid afforded the corresponding trialkylchlorosilanes in excellent yields. Similar treatment of trialkylsilanols with 35% aqueous hydrochloric acid also gave trialkylchlorosilanes in almost quantitative yields. The reaction of methyltrichlorosilane and dimethyldichlorosilane with alkyl-Grignard reagents bearing a bulky alkyl group, followed by treatment of the resulting mixtures with aqueous concentrated hydrochloric acid, produced the respective dialkylmethyl- and alkyldimethylchlorosilanes in high yields. Treatment of trialkylhydrosilanes with concentrated hydrochloric acid in the presence of a palladium catalyst afforded trialkylchlorosilanes in high yields.
Versatile method for introduction of bulky substituents to alkoxychlorosilanes
Masaoka, Shin,Banno, Tadashi,Ishikawa, Mitsuo
, p. 182 - 192 (2007/10/03)
The reactions of various alkoxytrichlorosilanes prepared in situ from tetrachlorosilane and alcohols, with Grignard reagents bearing a bulky substituent such as the isopropyl, sec-butyl, and cyclohexyl group afforded triisopropyl-, tri(sec-butyl)-, and tricyclohexylalkoxysilane in high yields. The reactions of n-butoxytrichlorosilane with these Grignard reagents produced triisopropyl-, tri(sec-butyl)-, and tricyclohexyl(n-butoxy)silane in 94%, 96%, and 92% yields, respectively. Methoxymethyldichlorosilane reacted with the same Grignard reagents to give diisopropyl-, di(sec-butyl)-, and dicyclohexylmethoxymethylsilane in 84%, 83%, and 83% yields. Treatment of methoxydimethylchlorosilane with the Grignard reagents readily afforded isopropyl-, sec-butyl-, and cyclohexylmethoxydimethylsilane in excellent yields. Similar treatment of methoxydimethylchlorosilane with tert-butylmagnesium chloride gave tert-butylmethoxydimethylsilane in 62% yield.
Hydrosilylation of cyclohexene and allyl chloride with trichloro-, dichloro(methyl)-, and chlorodimethylsilanes in the presence of Pt(0) complexes
Belyakova,Chernyshev,Storozhenko,Knyazev,Turkel'taub,Parshina,Kisin
, p. 925 - 930 (2008/02/03)
Hydrosilylation of cyclohexene and allyl chloride in the presence of Pt(0) complexes with tetramethyldivinyldisiloxane (Karstedt catalyst) and hexavinyldisiloxane was studied. It was shown that these catalysts are much more active in the hydrosilylation of cyclohexene with trichloro-, dichloro(methyl)-, and chlorodimethylsilane than the Pt(II)-containing Speier catalyst. In the hydrosilylation of allyl chloride in the presence of Pt(0) complexes, the ratio of the fraction of addition products to the fraction of reduction products increases from 5.7 (Speier catalyst) to 10-16. Quantum-chemical calculations showed that Pt(0) complexes are more active than Pt(II) complexes on the stage of formation of platinum silicon hydride complexes. Pleiades Publishing, Inc., 2006.
Hydrosilylation of cyclohexene, 1-methylcyclohexene, and isopropylidenecyclohexane
Yarosh,Zhilitskaya,Yarosh,Albanov,Voronkov
, p. 1895 - 1899 (2007/10/03)
Hydrosilylation of cyclohexene and isopropylidenecyclohexane with chloro(methyl)silanes Me3-n SiHCln (n = 1-3) gives rise to cyclohexyl- and chloro(2-cyclohexylpropyl)methylsilanes. Hydrosilylation of 1-methylcyclohexene with chlorodimethylsilane (n = 1) occurs anomalously and involves double-bond migration to form a mixture of seven compounds: the cis and trans isomers of 2-, 3-, 4-chlorodimethyl(methylcyclohexyl)silanes and chlorodimethyl(cyclohexylmethyl)silane. Chlorodimethylsilane (n = 2) adds to 1-methylcyclohexene to form a mixture of the cis and trans isomers of dichloro(methyl)(2-methylcyclohexyl)silane and dichloro(cyclohexylmethyl) methylsilane. With trichlorosilane (n = 3), no other products than trichloro(cyclohexylmethyl)silane are formed. The hydrosilylation products were reacted with ethynylmagnesium bromide to synthesize the corresponding ethynyl derivatives. 2004 MAIK "Nauka/Interperiodica".
SYNTHESIS AND PHOTOCHEMISTRY OF SILYLPHENYLPROPADIENES AND SILYLPHENYLPROPYNES
Fabry, L.,Goemoery, P.
, p. 291 - 296 (2007/10/02)
The synthesis and photoisomerization of the title compounds are described.Bis (silyl)-3-phenylpropyne yields a -photorearranged product of propadiene type, whereas tris(silyl)-3-phenylpropadiene is photochemically stable; however, a -thermal rea
Influence de la taille du cycle sur la substitution electrophile des cycloalkyltrimethylsilanes. Synthese de cycloalkyldimethylfluorosilanes
Grignon-Dubois, M.,Dunogues, J.,Calas, R.
, p. 291 - 295 (2007/10/02)
Cycloalkyltrimethylsilanes, excepting cyclopropyl-, react with electrophiles by Si - Me bond splitting.Consequently silicon can be functionalized by this route.We also propose a new synthesis of cycloalkyldimethylfluoro(or chloro-)silanes.In the case of five or six member ring derivates, the observed results are interpreted by a mechanism involving initial abstraction of hydride ion from the silicon substrate.
