A novel reduction of alcohols and ethers with a HSiEt3catalytic B(C6F5)3 system

Electrophilic Activation of Silicon–Hydrogen Bonds in Catalytic Hydrosilations

“…The B(C6F5)3 catalyst has since been applied to the hydrosilation of many substrates including olefins, [20] ketones, [19] and esters. [21] This catalyst is also useful for related transformations such as the reductive cleavage of C-O [22] and C-X [23] (X = halogen) bonds using hydridosilane reagents. Many other hydrosilation reactions appear to operate via polarization of the silane Si-H bond upon coordination to an electrophilic catalyst, with examples featuring main group Lewis acid catalysts (e.g.…”

“…[35] Related reactions, such as deoxygenation of alcohols and cleavage of alkyl ethers, are also catalyzed by B(C6F5)3 (Scheme 5, D and E) and represent convenient methods to cleave the strong C-O bonds of these substrates. [22] Although detailed mechanistic studies have not been performed for all of these transformations, the electrophilic silane activation pathway has been proposed to operate in these diverse processes. There have been extensive attempts to directly observe the Et3Si-H···B(C6F5)3 intermediate by low-temperature spectroscopic studies; however, this proposed intermediate has remained elusive.…”

Synthesis of vinyl substitute poly(silphenylene‐siloxane) via silyl hydride‐dialkoxysilane process

“…1 H-NMR and 29 Si-NMR were recorded on an INOVA 500 NMR spectrometer (Varian Co., Palo Alto, CA) at 400 ( 1 H), 99.3 MHz ( 29 Si), respectively, with CDCl 3 as solvent. TG curves were acquired on NETZSCH TG 209 (Netzch Co., Germany) at a heating rate of 108C/min, both the nitrogen and the air flow were 20 mL/min.…”

“…At such a low level of B(C 6 F 5 ) 3 , the silylium species will merely coordinate the more basic function group, i.e., methoxy, to produce polysiloxanes. 29 Si-NMR 29 Si-NMR can provide detailed information about the structure of the polysiloxanes. The 29 Si chemical shifts of the prepared polymer show four absorption peaks (Fig.…”

“…Silyl hydrides/B(C 6 F 5 ) 3 , generally Ph 3 SiH/B(C 6 F 5 ) 3 or Et 3 SiH/B(C 6 F 5 ) 3 is a useful system in organic chemistry, particularly in the transformation of aldehydes, ketones, alcohol, carboxylic acids, and their derivatives into silyl ethers or hydrocarbons. [20][21][22][23][24][25][26][27][28][29] B(C 6 F 5 ) 3 catalyzed coupling reaction of silyl hydrides with alkoxysilanes was a newly developed methods to prepare linear polysiloxanes by Rubinsztajn and coworkers. 30,31 This reaction takes place at or below room temperature in the presence of very low levels of B(C 6 F 5 ) 3 .…”