111197-93-4

Upstream product

• 103593-52-8 (S)-2-methylsulfonyloxy-1-(4-methylphenyl)-1-propanone dimethyl acetal 
• 67-56-1 methanol 
• 124709-72-4 (S)-(+)-2-(4'-methylphenyl)propanoic acid 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 201230-82-2 carbon monoxide 
• 938-94-3 (R,S)-2-(4'-methylphenyl) propionic acid 
• 18107-18-1 diazomethyl-trimethyl-silane 
• 75920-45-5 (+/-)-2-(4'-methylphenyl)-propionitrile 
• 624-31-7 4-tolyl iodide 
• 34880-70-1 [1-methoxyprop-1-enyloxy]trimethylsilane 
• 77-78-1 dimethyl sulfate 
• 66616-85-1 α-(4-methylphenyl)acrylic acid 
• 1429641-13-3 2-(p-tolyl)acryloyl chloride 
• 105457-91-8 2-oxo-2-(p-tolyl)acetyl chloride 

Downstream Products

• 93922-51-1 (S)-2-(4-methylphenyl)-1-propanol 

Relevant academic research and scientific papers

Palladium-Catalyzed Asymmetric Markovnikov Hydroxycarbonylation and Hydroalkoxycarbonylation of Vinyl Arenes: Synthesis of 2-Arylpropanoic Acids

Asymmetric hydroxycarbonylation is one of the most fundamental yet challenging methods for the synthesis of carboxylic acids. Herein, we reported the development of a palladium-catalyzed highly enantioselective Markovnikov hydroxycarbonylation of vinyl arenes with CO and water. A monodentate phosphoramidite ligand L6 plays vital role in the reaction. The reaction tolerates a range of functional groups, and provides a facile and atom-economical approach to an array of 2-arylpropanoic acids including several commonly used non-steroidal anti-inflammatory drugs. The catalytic system has also enabled an asymmetric Markovnikov hydroalkoxycarbonylation of vinyl arenes with alcohols to afford 2-arylpropanates. Mechanistic investigations suggested that the hydropalladation is irreversible and is the regio- and enantiodetermining step, while hydrolysis/alcoholysis is probably the rate-limiting step.

Enantioselective Hydrogen Atom Transfer: Discovery of Catalytic Promiscuity in Flavin-Dependent 'Ene'-Reductases

Flavin has long been known to function as a single electron reductant in biological settings, but this reactivity has rarely been observed with flavoproteins used in organic synthesis. Here we describe the discovery of an enantioselective radical dehalogenation pathway for α-bromoesters using flavin-dependent 'ene'-reductases. Mechanistic experiments support the role of flavin hydroquinone as a single electron reductant, flavin semiquinone as the hydrogen atom source, and the enzyme as the source of chirality.

Asymmetric Hydrogenation of α-Substituted Acrylic Acids Catalyzed by a Ruthenocenyl Phosphino-oxazoline-Ruthenium Complex

Asymmetric hydrogenation of various α-substituted acrylic acids was carried out using RuPHOX-Ru as a chiral catalyst under 5 bar H2, affording the corresponding chiral α-substituted propanic acids in up to 99% yield and 99.9% ee. The reaction could be performed on a gram-scale with a relatively low catalyst loading (up to 5000 S/C), and the resulting product (97%, 99.3% ee) can be used as a key intermediate to construct bioactive chiral molecules. The asymmetric protocol was successfully applied to an asymmetric synthesis of dihydroartemisinic acid, a key intermediate required for the industrial synthesis of the antimalarial drug artemisinin.

Pd/Josiphos-catalyzed enantioselective α-arylation of silyl ketene acetals and mechanistic studies on transmetalation and enantioselection

Palladium/(4-MeO-3,5-MePh)2PF-Pcy2) catalyzed the enantioselective arylation of silyl ketene acetals with iodoarenes in the presence of TlOAc to promote transmetalation of silyl ketene acetals. The highest enantioselectivities giving α-arylesters up to 91% ee were achieved when (E)-1-methoxy-1-(trimethylsiloxy)propene (E/Z = 88/12) was used for the silyl ketene acetal. The effect on enantioselection of a chiral ligand is discussed on the basis of the X-ray structure of the palladium/(4-MeO-3,5- MePh)2PF-Pcy2) complex and results of DFT computational studies on mechanistic aspects of the catalytic cycle.

Rational design of CH/π interaction sites in a basic resolving agent

A novel synthetic basic resolving agent, cis-1-aminobenz[f]indan-2-ol (ABI), was rationally designed by introducing effective CH/π interaction sites to cis-1-aminoindan-2-ol (AI), whose chiral recognition ability has been reported from our laboratory. ABI was applicable to a wide variety of racemic arylalkanoic acids and showed moderate to excellent chiral recognition ability, which was obviously higher than that of AI. The fundamental and important role of CH/π interactions, such as tunable CH(sp2)/π and CH(sp 3)/π interactions, in the chiral recognition by ABI was revealed by X-ray crystallographic study.

Enantioselective synthesis of (+)-nuciferal, (+)-(E)-nuciferol and (+)-α-curcumene by chiral hydrogenesterification reaction

Using chiral hydrogenesterification reaction as the key step, the stereoselective synthesis of (+)-nuciferal 1, (+)-(E)-nuciferol 2 and (+)-a-curcumene 3 has been achieved.

Enantioselective hydrolysis of various racemic α-substituted arylacetonitriles using Rhodococcus sp. CGMCC 0497

The enantioselective hydrolysis of 17 racemic α-substituted arylacetonitriles by Rhodococcus sp. CGMCC 0497 is described. The corresponding (R)-amides and (S)-acids were obtained with excellent enantiomeric excess in most cases. The effect of steric and electronic factors on the outcome of the reactions are discussed here. The results prove that nitrile-converting enzymes are efficient tools for the synthesis of sterically unencumbered chiral α-arylpropionic acids and amides.

A General Synthetic Method of Chiral 2-Arylalkanoic Esters via Thermal 1,2-Rearrangement

(S)-1-Aryl-2-sulfonyloxy-1-alkanone acetals, prepared from natural ethyl (S)-lactate or (S)-valine (chiral sources) by the use of a Grignard reaction, were rearranged under hydrolytic conditions in the presence of a base to give (S)-2-arylalkanoic esters which in general, showed much higher pharmacological activities than their antipodes.