42367-31-7

Upstream product

• 67-56-1 methanol 
• 629-05-0 n-octyne 
• 54583-19-6 2,2-dimethoxyoctane 

Downstream Products

• 78-93-3 butanone 
• 111-13-7 hexyl-methyl-ketone 

Relevant academic research and scientific papers

A step forward in solvent knitting strategies: Ruthenium and gold phosphine complex polymerization results in effective heterogenized catalysts

Porous polymers based on ruthenium and gold triphenylphosphine complexes (KPhos(Ru), KPhos(Ru)Bi, KPhos(AuCl) and KPhos(AuNTf2)) were prepared via a cost-effective solvent knitting method with [RuHClCO(PPh3)3] or AuXPPh3 (X = Cl, NTf2) as single monomers or combined with biphenyl, which represents a further approach to obtain heterogenized catalysts. The resulting materials mainly preserve the metal coordination environment of their parent complexes, are stable up to 350 °C and have reasonable surface areas (250-300 m2 g-1 for KPhos(Ru)-polymers). KPhos(Ru)s selectively catalyze the imination of alcohols in the presence of base and the results for KPhos(Au)s show they are effective for the intermolecular hydration and hydroamination of alkynes. These materials can be reused several times without significant loss of activity. This novel and simple method affords heterogenized catalysts that combine the reactivity and selectivity of their homogeneous counterparts with the stability and reusability of a heterogeneous framework.

Coupling Reaction of Enol Derivatives with Silyl Ketene Acetals Catalyzed by Gallium Trihalides

A cross-coupling reaction between enol derivatives and silyl ketene acetals catalyzed by GaBr3took place to give the corresponding α-alkenyl esters. GaBr3showed the most effective catalytic ability, whereas other metal salts such as BF3?OEt2, AlCl3, PdCl2, and lanthanide triflates were not effective. Various types of enol ethers and vinyl carboxylates as enol derivatives are amenable to this coupling. The scope of the reaction with silyl ketene acetals was also broad. We successfully observed an alkylgallium intermediate by using NMR spectroscopy, suggesting a mechanism involving anti-carbogallation among GaBr3, an enol derivative, and a silyl ketene acetal, followed by syn-β-alkoxy elimination from the alkylgallium. Based on kinetic studies, the turnover-limiting step of the reaction using a vinyl ether and a vinyl carboxylate involved syn-β-alkoxy elimination and anti-carbogallation, respectively. Therefore, the leaving group had a significant effect on the progress of the reaction. Theoretical calculations analysis suggest that the moderate Lewis acidity of gallium would contribute to a flexible conformational change of the alkylgallium intermediate and to the cleavage of the carbon?oxygen bond in the β-alkoxy elimination process, which is the turnover-limiting step in the reaction between a vinyl ether and a silyl ketene acetal.

Gallium tribromide catalyzed coupling reaction of alkenyl ethers with ketene silyl acetals

A 'Ga'llant couple: The α-alkenylation of esters was accomplished by GaBr3-catalyzed coupling between alkenyl ethers and ketene silyl acetals. In this reaction system, various alkenyl ethers, including those with vinyl and substituted alkenyl groups, were applicable, and the scope of applicable ketene silyl acetals was sufficiently broad. The mechanism is also discussed. Copyright

Regio- And stereoselective intermolecular hydroalkoxylation of alkynes catalysed by cationic gold(I) complexes

Vinyl ethers and ketals are obtained from the reaction of phenylacetylene derivatives and dimethyl acetylenedicarboxylate (DMAD) with alcohols in good yields and levels of stereoselectivity by using cationic gold(I)-phosphine complexes as catalysts. By choosing the appropriate phosphine, the selective formation of the Z or the E isomer of the vinyl ether can be tuned, and the undesired formation of the ketal can be controlled. The isomerisation of fumarates (Z-isomer) to maleates (E-isomer) is a gold-catalysed process that can be conducted in onepot. When using polyols, 5-membered cyclic ketals are easily isolated by extraction with hexane and the gold complex can be reused.

Triisobutylaluminun (TIBA) as a reagent to convert 2,2-dimethoxyalkanes to 2-methoxy-1-alkenes

Methanol ketals undergo methanol elimination by reaction with triisobutylaluminum to yield the corresponding less substituted 2-methoxyolefins; the experimental conditions are compatible with the presence of other functional groups.

Catalytic and Oxidative Methoxymercuration of Terminal Alkynes: Syntheses of 2-Methoxy-1-alkenes and 2-Methoxyacrolein Acetals

2-Methoxy-1-alkenes 2 are easily obtained by reaction of a variety of 1-alkynes with an excess of methanol in the presence of triethylamine and catalytic amounts of mercury(II) chloride.By changing the molar ratio of the reagents and increasing the reaction time, propargyl ethers undergo a further oxidative process to give the 2-methoxyacrolein acetals 3.

New Oxyfunctionalization Capabilities for ω-Hydroxylases: Asymmetric Aliphatic Sulfoxidation and Branched Ether Demethylation

Due to inherent difficulties in the chemical generation of aliphatic synthons, the stereo- and regioselective oxyfunctionalization of simple aliphatic substrates represents an area where chemical applications of biocatalysis would be particularly useful.The hydrocarbon monooxygenase from Pseudomonas oleovorans is a prototypical "ω-hydroxylase" known to carry out hydroxylation at the terminal methyl of alkanes as well as epoxidation of terminal olefins.It is now demonstrated that this enzyme system catalyzes stereoselective sulfoxidation of methyl thioether substrates, representing the first clear example of oxygenase-produced chiral aliphatic sulfoxides yet reported.In addition, it is shown that this enzyme system catalyzes oxygenative O-demethylation of branched alkyl methyl and branched vinyl methyl ethers to secondary alcohols and ketones, respectively.These findings establish new oxyfunctionalization capabilities, and thus a significantly expanded biotechnological potential, for the hydrocarbon monooxygenases.