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Upstream product

• 589-18-4 4-Methylbenzyl alcohol 
• 766-77-8 Dimethylphenylsilane 
• 104-87-0 4-methyl-benzaldehyde 

Relevant academic research and scientific papers

Efficient hydrosilylation of carbonyl compounds by 1,1,3,3-tetramethyldisiloxane catalyzed by Au/TiO2

1,1,3,3-Tetramethyldisiloxane (TMDS) is a highly reactive reducing reagent in the Au/TiO2-catalyzed hydrosilylation of carbonyl compounds relative to monohydrosilanes. The reduction of aldehydes or ketones with TMDS can be performed on many occ

Phosphirenium ions as masked phosphenium Catalysts: Mechanistic evaluation and application in synthesis

The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a "masked phosphenium"source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, Ha'SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electrondonating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies.

Efficient carbon-supported heterogeneous molybdenum-dioxo catalyst for chemoselective reductive carbonyl coupling

Reductive coupling of various carbonyl compounds to the corresponding symmetric ethers with dimethylphenylsilane is reported using a carbon-supported dioxo-molybdenum catalyst. The catalyst is air- and moisture-stable and can be easily separated from the reaction mixture for recycling. In addition, the catalyst is chemoselective, thus enabling the synthesis of functionalized ethers without requiring sacrificial ligands or protecting groups.

Efficient hydrosilylation of carbonyl compounds by 1,1,3,3-tetramethyldisiloxane catalyzed by Au/TiO2

1,1,3,3-Tetramethyldisiloxane (TMDS) is a highly reactive reducing reagent in the Au/TiO2-catalyzed hydrosilylation of carbonyl compounds relative to monohydrosilanes. The reduction of aldehydes or ketones with TMDS can be performed on many occasions at ambient conditions within short reaction times and at low loading levels of gold, whereas typical monohydrosilanes require excess heating and prolonged time for completion. The product yields are excellent, while almost stoichiometric amounts of carbonyl compounds and TMDS can be used. It is postulated that the enhanced reactivity of TMDS is attributed to the formation of a gold dihydride intermediate. This intermediate is also supported by the fact that double hydrosilylation of carbonyl compounds by TMDS is a negligible pathway.

Role of low-valent rhenium species in catalytic hydrosilylation reactions with oxorhenium catalysts

The catalytic competency of a Re(III) complex has been demonstrated. In the presence of silane, oxorhenium(V) catalysts are deoxygenated to produce species that are significantly more active than the metal oxo precursors in hydrosilylation reactions. The results presented suggest that, in evaluating mechanisms for catalytic hydrosilylation reactions that involve high-valent metal oxo complexes, the activity of species that may be generated by deoxygenation of the metal with silane should also be systematically investigated as potential catalysts.

On a new catalyzed silylation of alcohols by phenylhydrosilanes

KOH-18-crown-6 ether is a valuable system for the catalyzed dehydrocoupling of alcohols with phenylhydrosilanes (Ph3SiH and PhMe2SiH).