3553-88-6Relevant academic research and scientific papers
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
supporting information, 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.
Borane-Catalyzed Reductive α-Silylation of Conjugated Esters and Amides Leaving Carbonyl Groups Intact
Kim, Youngchan,Chang, Sukbok
supporting information, p. 218 - 222 (2016/01/25)
Described herein is the development of the B(C6F5)3-catalyzed hydrosilylation of α,β-unsaturated esters and amides to afford synthetically valuable α-silyl carbonyl products. The α-silylation occurs chemoselectively, thus leaving the labile carbonyl groups intact. The reaction features a broad scope of both acyclic and cyclic substrates, and the synthetic utility of the obtained α-silyl carbonyl products is also demonstrated. Mechanistic studies revealed two operative steps: fast 1,4-hydrosilylation of conjugated carbonyls and then slow silyl group migration of a silyl ether intermediate.
An efficient solvent-free route to silyl esters and silyl ethers
Ojima, Yuko,Yamaguchi, Kazuya,Mizuno, Noritaka
experimental part, p. 1405 - 1411 (2009/12/07)
Dinuclear metal complexes, especially (p-cymene)ruthenium dichloride dimer {[RuCl2(p-cymene)]2}, have been found to exhibit high catalytic performance for the dehydrosilylation of various kinds of carboxylic acids and alcohols. The dehydrosilylation with [RuCl2(p-cymene)] 2 proceeded efficiently with only one equivalent of silane with respect to substrate (carboxylic acids or alcohols) under solvent-free conditions to give the corresponding silyl esters and ethers in excellent yields with a high turnover number (TON) and frequency (TOF). The 1H NMR spectrum of a toluene-d8 solution of [RuCl2(p-cymene)] 2 and a silane showed a signal assignable to the ruthenium hydride species. In contrast, no new signals were detected in the 1H NMR spectrum of a toluene-d8 solution of [RuCl2(p-cymene)] 2 and a carboxylic acid or an alcohol. There-fore, the ruthenium metal in [RuCl2(p-cymene)]2 activates a silane to afford the hydride intermediate, possibly a silylmetal hydride species. Then, the nucleophilic attack of a substrate (carboxylic acid or alcohol) to the hydride intermediate proceeds to give the corresponding silylated product. The present dehydrosilylation with an optically active silane proceeded exclusively under inversion of stereochemistry at the chiral silicon center, suggesting that the nucleophilic attack of a substrate to the hydride intermediate occurs from the backside of the ruthenium-silicon bond.
Rhodium(II) Perfluorobutyrate Catalyzed Silane Alcoholysis. A Highly Selective Route to Silyl Ethers
Doyle, Michael P.,High, Kenneth G.,Bagheri, Vahid,Pieters, Roland J.,Lewis, Patricia J.,Pearson, Matthew M.
, p. 6082 - 6086 (2007/10/02)
Rhodium(II) perfluorobutyrate, Rh2(pfb)4, is an effective catalyst for the alcoholysis of trialkylsilanes at room temperature.Primary alcohols react with triethylsilane approximately 5 times faster than do secondary alcohols, and tertiary alcohols are virtually inert.Enhanced selectivity is achieved with tert-butyldimethylsilane.Hydrosilylation of olefinic alcohols is relatively unimportant even with terminal alkenes, but Rh2(pfb)4 does promote hydrogenation of 3-phenyl-2-propen-1-ol.Selected diols have been silylated with complete regioselectivity in Rh2(pfb)4-catalyzed reactions with either triethylsilane or tert-butyldimethylsilane.Methanolysis of (S)-(-)-1-naphthylphenylmethylsilane occurs with nearly complete inversion of configuration at silicon, and spectral analysis of the catalytic reaction suggests a mechanism for silane alcoholysis in which the rhodium(II) catalyst coordinates with the silicon hydride to activate silicon for backside nucleophilic attack by the alcohol.
METHYLPHENYLTRIPHENYLGERMYLSILANES FONCTIONNELS OPTIQUEMENT ACTIFS
Corriu, R. J. P.,Ould-Kada, S.,Lanneau, G.
, p. 23 - 38 (2007/10/02)
The structure of the unsymmetric compound MePh(X)SiGePh3 (X=H, F, Cl, OR) has been resolved.The stereochemistry of nucleophilic substitutions at silicon is not changed with Ph3Ge as substituent.Stereochemical correlations allow the determination of absolute configurations.
Silicon-Nitrogen Bonds. XXXIX. Kinetic Studies on the Spontaneous Hydrolysis, Alcoholysis, and Phenolysis of Silylamines
Kaufmann, K.-D.,Gisbier, D.,Grosse-Ruyken, H.,Ruehlmann, K.
, p. 721 - 728 (2007/10/02)
It could be shown by polarimetric and DC-metric methods that hydrolysis, alcoholysis, and phenolysis of silylamines are of second order and lead to equilibria.The rate of equilibrium establishment is determined by the position of a preceding protonation equilibrium and by steric effects.The position of the equilibria depends on inductive and steric effects.The enthalpy of activation for the ethanolysis of Me3SiNHPh was determined to 27,2 kJ/mol and the entropy of activation to -231 J/K*mol.The mechanism of the reactions is given.
