61418-99-3

Upstream product

• 776-76-1 methyldiphenylsilane 
• 98-86-2 acetophenone 
• 98-85-1 1-Phenylethanol 
• 1172-76-5 1,2-dimethyl-1,1,2,2-tetraphenyldisilane 
• 144-79-6 chloromethyldiphenylsilane 

Downstream Products

• 98-86-2 acetophenone 
• 98-85-1 1-Phenylethanol 
• 1445-91-6 (S)-1-phenylethanol 
• 1517-69-7 (R)-1-phenylethanol 

Relevant academic research and scientific papers

Exploration of the Fluoride Reactivity of Aryltrifluoroborate on Selective Cleavage of Diphenylmethylsilyl Groups

The first known report on the fluoride catalytic reactivity of potassium aryltrifluoroborate is described. The fluoride reactivity of phenyltrifluoroborate was controlled by substituents on the trifluoroborate-attached benzene, such as the methoxy group a

Cationic Ru-Se Complexes for Cooperative Si-H Bond Activation

The preparation and structural characterization of mononuclear tethered ruthenium(II) complexes of type [(DmpSe)Ru(PR3)]+BArF4- (DmpSe = 2,6-dimesitylphenyl selenolate, ArF = 3,5-bis(trifluoromethyl)phenyl) are described. Unlike relevant known selenolate

N-Heterocyclic Olefin Catalyzed Silylation and Hydrosilylation Reactions of Hydroxyl and Carbonyl Compounds

N-Heterocyclic olefins (NHOs), the alkylidene derivatives of N-heterocyclic carbenes (NHCs), have recently emerged as a new family of promising organocatalysts with strong nucleophilicity and Br?nsted basicity. The development of a novel method is shown using NHOs as efficient promoters for the direct dehydrogenative silylation of alcohols or hydrosilylation of carbonyl compounds. Preliminary results of the first NHO-promoted asymmetric synthesis are also discussed.

Rhodium-Catalyzed Dehydrogenative Silylation of Acetophenone Derivatives: Formation of Silyl Enol Ethers versus Silyl Ethers

A series of rhodium–NSiN complexes (NSiN=bis (pyridine-2-yloxy)methylsilyl fac-coordinated) is reported, including the solid-state structures of [Rh(H)(Cl)(NSiN)(PCy3)] (Cy=cyclohexane) and [Rh(H)(CF3SO3)(NSiN)(coe)] (coe=cis-cyclooctene). The [Rh(H)(CF3SO3)(NSiN)(coe)]-catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3SO3)(NSiN)(coe)] with HSiMe3and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si?H bond by a metal–ligand cooperative mechanism as the rate-determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2and the corresponding silyl enol ether.

Gold nanoparticles-catalyzed activation of 1,2-disilanes: Hydrolysis, silyl protection of alcohols and reduction of tert-benzylic alcohols

Gold nanoparticles supported on TiO2 catalyze under mild conditions the activation of a series of 1,2-disilanes towards hydrolysis and alcoholysis, with concomitant evolution of H2 gas. For the case of tert-benzyl alcohols, the main or only pathway is reduction to the corresponding alkanes.

Base-free dehydrogenative coupling of enolizable carbonyl compounds with silanes

A dehydrogenative coupling between enolizable carbonyl compounds and equimolar amounts of triorganosilanes catalyzed by a tethered ruthenium complex with a Ru-S bond is reported. The complex is assumed to fulfill a dual role by activating the Si-H bond to release a silicon electrophile and by abstracting an α-proton from the intermediate silylcarboxonium ion, only liberating dihydrogen as the sole byproduct. Reaction rates are exceedingly high at room temperature with very low loadings of the ruthenium catalyst.

An axially chiral, electron-deficient borane: Synthesis, coordination chemistry, Lewis acidity, and reactivity

An axially chiral dihydroborepine with a binaphthyl backbone and a C 6F5 substituent at the boron atom was prepared by transmetalation from the corresponding tin precursor. This novel motif was structurally characterized by X-ray diffraction analysis as its THF and its PhCN Lewis acid/base complex. 1H NMR measurements at variable temperatures of the former adduct revealed a remarkable dynamic behavior in solution. Several more Lewis pairs with oxygen, nitrogen, carbon, and phosphorus σ-donors were synthesized and analyzed by multinuclear NMR spectroscopy. The determination of the borane's Lewis acidity with the Gutmann-Beckett method attests its substantial Lewis acidity [85% with Et3PO as well as 74% with Ph3PO relative to the parent B(C6F5) 3]. Representative examples of SiH bond activation (carbonyl reduction and dehydrogenative SiO coupling) are included, demonstrating the chemical stability and the synthetic potential of the new chiral boron-based Lewis acid. Copyright

Analysis of the enantioselectivities and initial rates of the hydrosilylation of acetophenone catalyzed by [Rh(cod)Cl]2/(chiral diphosphine). The quantitative analysis of ligand effects

Through the application of the quantitative analysis of ligand effects (QALE) method to the study of the hydrosilylation of acetophenone, we have shown, for the first time, that the initial rate and enantioselectivity of a complicated catalytic system responds in a rational manner to the variations in the stereoelectronic properties of the silane. The reactions (in benzene-d6 at 63 °C) were catalyzed by [Rh(cod)Cl]2/(chiral diphosphine) (chiral diphosphine=(R)-BINAP [(R)-(+)-2,2′-bis(diphenylphosphino)- 1,1′binaphthyl], (R,R)-tolyl-BINAP [(R)-(+)-2,2′-bis (di-p-tolylphosphino)-1,1′-binaphthyl], (R,R)-Me-DUPHOS [(R,R )-(-)-1,2-Bis-2,5-dimethylphospholano)benzene], (R,R)-DIOP [(R,R)-(-)-2,3-O-isopropylidine-2,3-dihydroxy-1,4-bis(diphenylphosphino) butane], and (R)-QUINAP [(R)-(+)-1-(2-diphenylphosphino-1-naphthyl) isoquinoline]. The ee's (R) of the hydrosilylation products (CH3CH(OSiR3)Ph) range between - 9 and 53% with the (R)-QUINAP giving the poorest enantioselectivity. The QALE analyses of log( R/S) for (R)-BINAP, (R)-tolyl-BINAP, (R,R)-Me-DUPHOS, and (R,R)-DIOP reveal that the steric effects associated with the silanes are not monotonic.