58864-04-3

Upstream product

• 766-77-8 Dimethylphenylsilane 
• 555-16-8 4-nitrobenzaldehdye 
• 619-73-8 4-nitrobenzyl chloride 

Relevant academic research and scientific papers

[MoO2Cl2] as catalyst for hydrosilylation of aldehydes and ketones

The high valent molybdenum-dioxo complex [MoO2Cl2] catalyzes the addition of dimethylphenylsilane to aldehydes and ketones to afford the corresponding dimethylphenylsilyl ethers in quantitative yield.

HYDROXIDE-CATALYZED FORMATION OF SILICON-OXYGEN BONDS BY DEHYDROGENATIVE COUPLING OF HYDROSILANES AND ALCOHOLS

The present disclosure is directed to methods for dehydrogenatively coupled hydrosilanes and alcohols, the methods comprising contacting an organic substrate having at least one organic alcohol moiety with a mixture of at least one hydrosilane and sodium and/or potassium hydroxide, the contacting resulting in the formation of a dehydrogenatively coupled silyl ether. The disclosure further described associated compositions and methods of using the formed products.

Sodium Hydroxide Catalyzed Dehydrocoupling of Alcohols with Hydrosilanes

An O-Si bond construction protocol employing abundantly available and inexpensive NaOH as the catalyst is described. The method enables the cross-dehydrogenative coupling of an alcohol and hydrosilane to directly generate the corresponding silyl ether under mild conditions and without the production of stoichiometric salt byproducts. The scope of both coupling partners is excellent, positioning the method for use in complex molecule and materials science applications. A novel Si-based cross-coupling reagent is also reported.

Lewis acidity of bis(perfluorocatecholato)silane: Aldehyde hydrosilylation catalyzed by a neutral silicon compound

Bis(perfluorocatecholato)silane Si(catF)2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N′-diisopropylbenzamide. The potent Lewis acidity of Si(catF)2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu4BArF4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfer occurs prior to silicon-oxygen bond formation.

Homobimetallic rhodium NHC complexes as versatile catalysts for hydrosilylation of a multitude of substrates in the presence of ambient air

Two recently reported air- and water-stable di-Rh complexes based on 1,3-bis(3′-butylbenzimidazol-2′-ylidene)benzene were utilized as catalysts for hydrosilylation. Among the substrates investigated were aldehydes, ketones, α,β-unsaturated carbonyls, acyl chlorides, nitriles, alkenes, nitro groups, isocyanates, and tertiary amides. Additionally, carbon dioxide underwent hydrosilylation to produce dimethylphenylsilylformate. The catalysts compared well to other previously reported hydrosilylation catalysts, and the Rh-Cl catalyst was found to be faster and more selective than the Rh-I complex in each case.

Analysis of an unprecedented mechanism for the catalytic hydrosilylation of carbonyl compounds

This work details an in-depth evaluation of an unprecedented mechanism for the hydrosilylation of carbonyl compounds catalyzed by (PPh3) 2Re(O)2I. The proposed mechanism involves addition of a silane Si-H bond across one of the rhenium-oxo bonds to form siloxyrhenium hydride intermediate 2 that reacts with a carbonyl substrate to generate siloxyrhenium alkoxide 4, which, in turn, affords the silyl ether product. Compelling evidence for the operation of this pathway includes the following: (a) isolation and structural characterization by X-ray diffraction of siloxyrhenium hydride intermediate 2, (b) demonstration of the catalytic competence of intermediate 2 in the hydrosilylation reaction, (c) 1H and 31P{1H} NMR and ESI-MS evidence for single-turnover conversion of 2 into 1, (d) observation of intermediate 2 in the working catalyst system, and (e) kinetic analysis of the catalytic hydrosilylation of carbonyl compounds by 1.

Dioxomolybdenum(VI) complexes as catalysts for the hydrosilylation of aldehydes and ketones

The dioxomolybdenum(vi) complexes [MoO2Cl2] (1), [MoO2(acac)2] (2), [MoO2(S2CNEt 2)2] (3), [CpMoO2Cl] (4), [MoO 2(mes)2] (5) and the p

Reversing the role of the metal - oxygen π-bond. Chemoselective catalytic reductions with a rhenium(V)-dioxo complex

The metal-oxygen bond plays a critical role in some of the most important biological and synthetic reactions. However, the majority of these processes result in the oxidation of the target organic substrate; applications of this class of metal complexes to other organic transformations are extremely rare. In this paper, we report a new type of catalytic process in which complexes with metal-oxygen multiple bonds are used as reductants rather than oxidants. The overall reaction provides a highly chemoselective reduction/protection of carbonyl groups. In addition to providing a new way of catalyzing organic reactions, these catalysts can be used in the presence of a wide range of other functional groups such as amino, cyano, nitro, aryl halo, ester, and alkene; unlike many of their late metal relatives, they are inexpensive as well as air and moisture tolerant. Copyright

Hydrosilylation of aldehydes and ketones catalyzed by [Ph3P(CuH)]6

Exposure of an aldehyde or ketone to ≤ 5 mol% (in copper) of Stryker's reagent [Ph3P(CuH)]6 in the presence of one of several silanes affords the corresponding protected alcohol in high yields. Aldehydes can be cleanly reduced in the presence of ketones.