114937-30-3

Upstream product

• 194606-27-4 (-)-2-(4-isobutylphenyl)-1-acetoxypropane 
• 194606-25-2 Acetic acid (S)-2-(4-isobutyl-phenyl)-3-(toluene-4-sulfonyloxy)-propyl ester 
• 51146-56-6 (S)-ibuprofen 
• 56374-24-4 (R/S)-4-isobutyl-α-methylstyrene oxide 
• 51407-46-6 2-(4-isobutylphenyl)propionaldehyde 
• 61566-34-5 (+/-)-ibuprofen methyl ester 
• 63444-56-4 p-isobutylstyrene 
• 38861-78-8 1-(4-isobutyl-phenyl)-ethanone 
• 36039-36-8 2-(4-isobutylphenyl)propan-1-ol 
• 98-88-4 benzoyl chloride 
• 272458-63-6 (S)-ethyl 2-(4-isobutylphenyl)propanoate 
• 15687-27-1 ibuprofen 
• 124-38-9 carbon dioxide 
• 1262241-05-3 C₂₈H₃₀N₂OS 

Downstream Products

• 51146-56-6 (S)-ibuprofen 
• 15687-27-1 ibuprofen 
• 114937-04-1 (4R)-2-<(1S)-1-(4-(2-Methylpropyl)phenyl)ethyl>thiazolidine-4-carboxylic Acid 
• 51146-57-7 (R)-ibuprofene 
• 110773-62-1 S-2-(p-isobutylphenyl)propionaldehyde 

Relevant academic research and scientific papers

Manganese Catalyzed Hydrogenation of Enantiomerically Pure Esters

A manganese-catalyzed hydrogenation of esters has been accomplished with TONs up to 1000, using cheap, environmentally benign, potassium carbonate and simple alcohols as activator and solvent, respectively. The weakly basic conditions lead to good functional group tolerance and enable the hydrogenation of enantiomerically enriched α-chiral esters with essentially no loss of stereochemical integrity.

A modification of the asymmetric dihydroxylation approach to the synthesis of (S)-2-arylpropanoic acids

Catalytic hydrogenolysis of (S)-2-phenyl-1-2-propanediol (2), prepared by an asymmetric dihydroxylation of α-methylstyrene (1) with AD-mix-α, over Pearlman's catalyst gave (S)-2-phenyl-1-propanol (3). This method was applied to the synthesis of optically active 2-arylpropanoic acid antiinflammatory agents, (S)-ibuprofen (8) and (S)-naproxen (13).

Chemoenzymatic synthesis of antiinflammatory drugs in enantiomerically pure form

A novel chemoenzymatic route to chiral antiinflammatory drugs in enantiomerically pure form is described. Copyright (C) 2000 Elsevier Science Ltd.

Chiral Recognition between a Substituted Cyclooctatetraene Dianion and a Half Crown Ether Substituted with Ibuprofen

(S)-Verbenol was substituted onto cyclooctatetraene (COT) via an ether linkage. In tetrahydrofuran (THF), Cs+ or Na+ counterions are tightly ion associated with the verbenoxy-COT dianion. A cosolvent, consisting of an ibuprofen unit connected to a half crown ether, was added to the verbenoxy-COT2-,M+2 solutions. The intimate interaction between the chiral cosolvent (ibuprofoxymethoxyethoxyethane) and the ion-associated counterion (either Na+ or Cs+) forces a chiral recognition between the verbenoxy moiety and the ibuprofoxy moiety. When a molar excess of the cosolvent is present in the dianion THF solution, separation of the cosolvent associated with the verbenoxy-COT2-,M+2 complex from the uncomplexed cosolvent allows partial resolution of the enantiomers of ibuprofoxymethoxyethoxyethane.

Integrated Experimental and Computational Studies on the Organocatalytic Kinetic Resolution of β-Unfunctionalized Primary Alcohols Using a Chiral 1,2-Diamine: The Importance of Noncovalent Interactions

The enantioselective kinetic resolution of β-unfunctionalized primary alcohols with benzoyl chloride was carried out in the presence of a catalytic amount of a novel chiral 1,2-diamine derived from (S)-proline. Several valuable chiral 2-substituted propan-1-ols were obtained with good enantioselectivities. Density functional theory calculations revealed that the noncovalent interaction, such as CH-πinteraction, is crucial for the enantioselectivity of the resolution. This study was conducted through an interplay between experiment and computation.

Unexpected CNN-to-CC Ligand Rearrangement in Pincer-Ruthenium Precatalysts Leads to a Base-Free Catalyst for Ester Hydrogenation

We report the conversion of a series of CNN-pincer-ruthenium complexes Ru(CNN)HCl(CO) to a CC-chelated form Ru(CC)(PR3)2H(CO) on reaction with sodium tert-butoxide and monodentate phosphines. When the phosphine is triphenylphosphine, cis-phosphine complexes form at room temperature, which convert to the trans isomer at elevated temperatures. When the phosphine is tricyclohexylphosphine, only the trans-phosphine isomer is observed. The CC-chelated complexes are active catalysts for the hydrogenation of esters, without the need for added base. The ligand structure-activity relationship in the series of CC-chelated complexes mirrors that in the precursor CNN-Ru complexes, potentially indicating a common catalytic mechanism. Density functional theory calculations establish a plausible mechanism for the CNN-to-CC rearrangement and demonstrate that this rearrangement is potentially reversible under the conditions of ester hydrogenation catalysis.

MANGANESE-CATALYSED HYDROGENATION OF ESTERS

The present invention relates to the field of catalytic hydrogenation and, more particularly, to methods of manganese-catalysed hydrogenation of esters to alcohols. Advantageously, where the esters are chiral, the hydrogenations proceed with high or complete stereochemical integrity..

Dehydroalkylative Activation of CNN- A nd PNN-Pincer Ruthenium Catalysts for Ester Hydrogenation

Ruthenium-pincer complexes bearing CNN- A nd PNN-pincer ligands with diethyl-or diisopropylamino side groups, which have previously been reported to be active precatalysts for ester hydrogenation, undergo dehydroalkylation on heating in the presence of tricyclohexylphosphine to release ethane or propane, giving five-coordinate ruthenium(0) complexes containing a nascent imine functional group. Ethane or propane is also released under the conditions of catalytic ester hydrogenation, and time-course studies show that this release is concomitant with the onset of catalysis. A new PNN-pincer ruthenium(0)-imine complex is a highly active catalyst for ester hydrogenation at room temperature, giving up to 15500 turnovers with no added base. This complex was shown to react reversibly at room temperature with two equivalents of hydrogen to give a ruthenium(II)-dihydride complex, where the imine functionality has been hydrogenated to give a protic amine side group. These observations have potentially broad implications for the identities of catalytic intermediates in ester hydrogenation and related transformations.

Biocatalytic Parallel Interconnected Dynamic Asymmetric Disproportionation of α-Substituted Aldehydes: Atom-Efficient Access to Enantiopure (S)-Profens and Profenols

The biocatalytic asymmetric disproportionation of aldehydes catalyzed by horse liver alcohol dehydrogenase (HLADH) was assessed in detail on a series of racemic 2-arylpropanals. Statistical optimization by means of design of experiments (DoE) allowed the identification of critical interdependencies between several reaction parameters and revealed a specific experimental window for reaching an ′optimal compromise′ in the reaction outcome. The biocatalytic system could be applied to a variety of 2-arylpropanals and granted access in a redox-neutral manner to enantioenriched (S)-profens and profenols following a parallel interconnected dynamic asymmetric transformation (PIDAT). The reaction can be performed in aqueous buffer at ambient conditions, does not rely on a sacrificial co-substrate, and requires only catalytic amounts of cofactor and a single enzyme. The high atom-efficiency was exemplified by the conversion of 75 mM of rac-2-phenylpropanal with 0.03 mol% of HLADH in the presence of ～0.013 eq. of oxidized nicotinamide adenine dinucleotide (NAD+), yielding 28.1 mM of (S)-2-phenylpropanol in 96% ee and 26.5 mM of (S)-2-phenylpropionic acid in 89% ee, in 73% overall conversion. Isolated yield of 62% was obtained on 100 mg-scale, with intact enantiopurities. (Figure presented.).

Highly Regio- and Enantioselective Copper-Catalyzed Reductive Hydroxymethylation of Styrenes and 1,3-Dienes with CO2

Herein, we report a highly regio- and enantioselective copper-catalyzed reductive hydroxymethylation of styrenes and 1,3-dienes with 1 atm of CO2. Diverse important chiral homobenzylic alcohols were readily prepared from styrenes. Moreover, a variety of 1,3-dienes also were converted to chiral homoallylic alcohols with high yields and excellent regio-, enantio-, and Z/E-selectivities. The utility of this transformation was demonstrated by a broad range of styrenes and 1,3-dienes, facile product modification, and synthesis of bioactive compounds (R)-(-)-curcumene and (S)-(+)-ibuprofen. Mechanistic studies demonstrated the carboxylation of phenylethylcopper complexes with CO2 as one key step.