1028-61-1Relevant academic research and scientific papers
Nonclassical ruthenium silyl dihydride complexes TpRu(PPh 3)(I?·3-HSiR3H) [Tp = hydridotris(pyrazolyl)borate]: Catalytic hydrolytic oxidation of organosilanes to silanols with TpRu(PPh3)(I?·3-HSiR 3H)
Lee, Ting Yan,Dang, Li,Zhou, Zhongyuan,Yeung, Chi Hung,Lin, Zhenyang,Lau, Chak Po
, p. 5675 - 5684 (2010)
An X-ray crystallographic study showed that it is more appropriate to describe the complexes TpRu(PPh3)"H2SiR 3" as TpRu(PPh3)(I?·3- HSiR3H), a static structure containing HA?·A? ·A?·SiA?·A?·A?·H bonding rather than a highly fluxional pair ofI?-silane hydride species TpRu(PPh3)(Ha)(I?·2-H bSiR3) [rlhar2] TpRu(PPh3)(H b)(I?·2-HaSiR3). One of the complexes was used for the catalytic hydrolytic oxidation of organosilanes to silanols. A mechanism, which does not involve the usual oxidative addition of silane to the metal center to form the silyl hydride species, is proposed, which is supported by theoretical calculations.
Selective Manganese-Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions
Wang, Kaikai,Zhou, Jimei,Jiang, Yuting,Zhang, Miaomiao,Wang, Chao,Xue, Dong,Tang, Weijun,Sun, Huamin,Xiao, Jianliang,Li, Chaoqun
, p. 6380 - 6384 (2019/05/06)
The first manganese-catalyzed oxidation of organosilanes to silanols with H2O2 under neutral reaction conditions has been accomplished. A variety of organosilanes with alkyl, aryl, alknyl, and heterocyclic substituents were tolerated, as well as sterically hindered organosilanes. The oxidation appears to proceed by a concerted process involving a manganese hydroperoxide species. Featuring mild reaction conditions, fast oxidation, and no waste byproducts, the protocol allows a low-cost, eco-benign synthesis of both silanols and silanediols.
Highly selective oxidation of organosilanes to silanols with hydrogen peroxide catalyzed by a lacunary polyoxotungstate
Ishimoto, Ryo,Kamata, Keigo,Mizuno, Noritaka
supporting information; experimental part, p. 8900 - 8904 (2010/01/16)
Silanol synthesis: Divacant lacunary polyoxotungstate (nBu4N+)4[g- SiW10O34(H2O)2] (I) is an efficient homogeneous catalyst for highly selective oxidation of organosilanes to silanols with 30/60% aqueous H2O2. Various kinds of silanes 1 containing aryl, alkyl, alkenyl, alkynyl and alkoxy groups are chemoselectively converted into the corresponding silanols 2 in high yields with only one equivalent of aqueous H2O2 with respect to the substrate.
Oxyfunctionalization reactions by perfluoro cis-2,3-dialkyloxaziridines. Enantioselective conversion of silanes into silanols
Cavicchioli, Marcello,Montanari, Vittorio,Resnati, Giuseppe
, p. 6329 - 6330 (2007/10/02)
Perfluoro cis-2,3-dialkyloxaziridine 2 is shown to perform the oxyfunctionalization of silanes 1 under very mild conditions to give silanols and silanediols 3 in high chemical yields and complete enantioselectivity.
THE PREPARATION AND CHEMISTRY OF (R)-(1-NAPHTYL)PHENYLMETHYLSILYLMETHYLLITHIUM: STEREOCHEMISTRY AT SILICON IN THE ELIMINATION OF β-HYDROXYSILANES
Larson, Gerald L.,Prieto, J. Antonio,Ortiz, Edgardo
, p. 3781 - 3790 (2007/10/02)
(R)-(1-naphthyl)phenylmethylsilylmethyllithium has been prepared from 1-naphthylphenylmethylsilylmethyltri-n-butyltin, which is in turn prepared in four steps from (R)-(1-naphthyl)phenylmethylsilane.The title lithium reagent was reacted with benzaldehyde, pivaldehyde, acrolein and 2-methylcyclohexanone to produce the corresponding β-hydroxysilanes in good yield, but with only a 3-4percent diastereomeric excess.Unfortunately, these diastereomers proved impossible to separate.Model studies employing the methyldiphenylsilyl group showed that these β-hydroxysilanes could be protiodesilylated to give the corresponding methyl alcohol.The products from the adduct with pivaldehyde and acrolein were used to investigate the stereochemistry at silicon of the β-hydroxysilanes.This was found to occur with inversion of configuration at silicon when the elimination is carried out with boron fluoride etherate, sulfuric acid or acetic acid/sodium acetate, but with retention of configuration when carried out with potassium hydride.
