1432-39-9

Upstream product

• 33664-05-0 (p-Methoxy-phenyl)-dimethyl-fluor-silan 
• 75-54-7 Dichloromethylsilane 
• 676-58-4 methylmagnesium chloride 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 1066-35-9 dimethylmonochlorosilane 
• 106-38-7 para-bromotoluene 
• 2417-95-0 p-tolyllithium 

Downstream Products

• 52328-42-4 (Dimethyl-p-tolyl-silanyl)-acetic acid methyl ester 
• 57733-86-5 p-Tolyldimethyldichlormethylsilan 
• 834-14-0 p-benzylanizole 
• 134310-80-8 C₉H₁₄O₃Si 
• 17920-15-9 (4-methylphenyl)dimethylsilanol 
• 945627-97-4 (Z)-4-methyl-4-tert-butyl-3-[(dimethyl-p-tolylsilyl)methylene]-3-(p-tosyl)-1-azetidin-2-one 
• 688-73-3 tri-n-butyl-tin hydride 
• 18055-70-4 1,3-bis(4′-tolyl)-1,1,3,3-tetramethyldisiloxane 
• 51501-87-2 dimethyl(4-methylphenyl)methoxysilane 
• 106-44-5 p-cresol 
• 52392-64-0 n-butyl cinnamate 
• 64437-82-7 ethyl 2-(dimethyl(p-tolyl)silyl)acetate 

Relevant academic research and scientific papers

METHOD OF PREPARING SILANOLS WITH SELECTIVE CYTOCHROME P450 VARIANTS AND RELATED COMPOUNDS AND COMPOSITIONS

This disclosure provides a method of preparing a silanol-functional organosilicon compound with a cytochrome P450 variant that facilitates the oxidization of a silyl hydride group to a silanol group in the presence of oxygen. The method includes combining the cytochrome P450 variant and an organosilicon compound having at least one silicon-bonded hydrogen atom to give a reaction mixture and exposing the reaction mixture to oxygen to oxidize the organosilicon compound, thereby preparing the silanol-functional organosilicon compound. Cytochrome P450 variants suitable for use in the method are also disclosed, along with methods for engineering and optimizing the same. Nucleic acids encoding the cytochrome P450 variants and compositions, expression vectors, and host cells including the same are also disclosed.

Au Nanoparticle-Catalyzed Insertion of Carbenes from α-Diazocarbonyl Compounds into Hydrosilanes

Supported Au nanoparticles on TiO2 catalyze the insertion of carbenes from α-diazocabonyl compounds into hydrosilanes. It is proposed that the transformation involves two modes of catalytic activation: formation of nucleophilic Au carbenes on the surface of nanoparticle via expulsion of N2 and activation of the Si-H bond of hydrosilane on Au nanoparticle, followed by coupling of the chemisorbed species. No external ligands or additives are required, while the process is purely heterogeneous, thus allowing the recycling and reuse of the catalyst.

Ru(ii)-Pheox-catalyzed Si-H insertion reaction: construction of enantioenriched carbon and silicon centers

We established a highly enantioselective Si-H insertion reaction to construct chiral centers at the carbon and silicon atoms, using a Ru(ii)-pheox catalyst. The catalytic asymmetric Si-H insertion reaction of α-methyl-α-diazoesters proceeded smoothly with excellent stereoinduction at both the neighboring carbon and silicon atoms (up to 99% yield and 99% ee).

Heme Protein Catalysts for Carbon-Silicon Bond Formation In Vitro and In Vivo

The present invention provides compositions and methods for catalyzing the formation of carbon-silicon bonds using heme proteins. In certain aspects, the present invention provides heme proteins, including variants and fragments thereof, that are capable of carrying out in vitro and in vivo carbene insertion reactions for the formation of carbon-silicon bonds. In other aspects, the present invention provides methods for producing an organosilicon product, the method comprising providing a silicon-containing reagent, a carbene precursor, and a heme protein; and combining the components under conditions sufficient to produce an organosilicon product. Host cells expressing the heme proteins are also provided by the present invention.

Synthesis of phenols via fluoride-free oxidation of arylsilanes and arylmethoxysilanes

Rapid, efficient methods have been developed to prepare phenols from the oxidation of arylhydrosilanes. The effects of arene substituents and fluoride promoters on this process show that while electron-deficient arenes can undergo direct oxidation from the hydrosilane, electron-rich aromatics benefit from silane activation via oxidation to the methoxysilane using homogeneous or heterogeneous transition metal catalysis. The combination of these two oxidations into a streamlined flow procedure involving minimal processing of reaction intermediates is also reported.

Fluoride-Promoted Rearrangement of Organo Silicon Compounds: A New Synthesis of 2-(Arylmethyl)aldehydes from 1-Alkynes

A new approach to 2-(arylmethyl)aldehydes 4 based upon a 1,2-anionotropic rearrangement of an aryl group is presented. The synthetic sequence begins with a silylformylation reaction of terminal acetylenes 5 with aryl and heteroaryl silanes 6, followed by treatment of the products (Z)-1 with TBAF. The optimization of the experimental conditions of the fluoride-promoted step is described, together with the synthetic potentialities of the process. A plausible mechanism of the rearrangement reaction is reported that suggests the addition of the fluoride ion to the arylsilicon moiety of β-silylalkenals (Z)-1 and the consequent migration of the aryl group to the adjacent carbon atom. Both aryl and heteroaryl substituents can rearrange without any loss of configuration. Bromofunctionalized substrates undergo an intramolecular reaction that affords exclusively carbacyclobenzyl aldehydes, further enhancing the high synthetic value of this method.

Stereocontrol in organic synthesis using silicon-containing compounds. Syntheses of (±)-2-deoxyribonolactone and (±)-arabonolactone

Samarium iodide reacts with methyl (Z)-3-dimethyl(4-methylphenyl)silylprop-2-enoate 5b to give dimethyl (3RS,4SR)-3,4-bis[dimethyl(4-methylphenyl)silyl]hexane-1,6-dioate 8b with high stereoselectivity. This meso diester can be converted into (3RS,4SR)-3,4-bis[dimethyl(4-methylphenyl)silyl]pentan-5-olide 16 by Dieckmann cyclisation, demethoxycarbonylation and Baeyer-Villiger reaction. Silyl-to-hydroxy conversion and relactonisation gave (±)-deoxyribonolactone, and anti-selective enolate hydroxylation followed by silyl-to-hydroxy conversion gave (±)-arabonolactone. An attempt to synthesise sugars with the relative configuration (3RS,4RS) was thwarted by an unprecedented retention of configuration at the migration origin in the cationic rearrangement of (3RS,4SR)-3,4-bis[dimethyl(4-methylphenyl)silyl]-5-hydroxypentanoic acid 28 to (3RS,4SR)-3,5-bis[dimethyl(4-methylphenyl)silyl]pentan-1,4-olide 30.

Kinetic Control in the Cleavage of Unsymmetrical Disilanes

A series of 12 phenyl-substituted arylpentamethyldisilanes 1a-1 have been synthesized in order to examine the regioselectivity of their nucleophilic Si,Si bond cleavage reactions under Still's conditions (MeLi/HMPA/0°C). It has been found that the sensitivity of these reactions to the electronic effects of the substituents in the phenyl ring could be described by the Hammett-type equation log(kA/kB) = 0.4334 + 2.421(Σσ); (correlation coefficient R = 0.983). The kA/kB ratio represents the relative rate of attack at silicon atom A (linked to the aryl ring) or at silicon atom B (away from the aryl ring) of the unsymmetrical disilanes. Thus, the present investigation shows that the earlier belief according to which the nucleophilic cleavage of unsymmetrical disilanes always produces the more stable silyl anionic species (thermodynamic control) should be abandoned, or at least seriously amended: kinetic factors appear to exert a primary influence on the regioselectivity of such reactions. Since the two major kinetic factors (i.e., electrophilic character of and steric hindrance at a given silicon atom) have opposite effects on the orientation of the reaction, it may happen that kinetic and thermodynamic control lead to the same result. For some of the unsymmetrical disilanes studied, the major reaction path was not the Si,Si bond cleavage; instead, Si-aryl bond breaking occurred, producing the corresponding aryl anions.

Failure in Several Attempts to Prepare Arylsilyl-lithium Reagents by the Gilman Cleavage of Disilanes with Lithium

Several diarylsilanes 5,9 and 11 do not cleave with lithium in THF to give silyl-lithium reagents, in contrast to diphenyltetramethyldisilane 2, which is well known to give phenyldimethylsilyl-lithium.Trityldiphenylsilyl bromide 13 reacts with lithium to

Fluoride Ion Catalyzed Reduction of Aldehydes and Ketones with Hydrosilanes. Synthetic and Mechanistic Aspects and an Application to the Threo-Directed Reduction of α-Substituted Alkanones

Reduction of aldehydes and ketones with hydrosilanes proceeded in the presence of a catalytic amount of tetrabutylammonium fluoride or tris(diethylamino)sulfonium difluorotrimethylsilicate in aprotic polar solvents under mild conditions.A significant isotope effect (kH/kD = 1.50) was observed in competitive reduction of acetophenone with HSiMe2Ph and DSiMe2Ph.The reaction was of first order in the concentration of an aprotic polar solvent HMPA.Reduction of 2-methylcyclohexanone gave cis-2-methylcyclohexanol with selectivities up to 95percent.The kinetic and stereochemical results suggest that a hexavalent fluorosilicate - is involved. α-Alkoxy (acyloxy or dimethylamino) ketones were transformed to threo alcohols in high diastereoselectivities.The reduction was also applied to α-methyl-β-keto amides, RCOCH(MeCONR)2, to afford the corresponding threo alcohols in >98percent selectivity.The threo selectivity is explained in terms of the Felkin-Anh model in which interaction of carbonyl oxygen with a countercation is ideally suppressed.The threo-directed reduction was applied to (R)-1-phenyl-4-(2-tetrahydropyranyloxy)-1-penten-3-one and N-(2-benzoylpropanoyl)piperidine.The resulting threo alcohols were respectively converted into (2R,3S)-2,3-(cyclohexylidenedioxy)butanal, a key intermediate of daunosamine synthesis, and into a pharmacologically useful compound threo-N-(3-hydroxy-2-methyl-3-phenylpropyl)piperidine.