13511-29-0

Upstream product

• 7138-34-3 p-chloromandelic acid 
• 64-17-5 ethanol 
• 14062-24-9 4-chloro-benzeneacetic acid, ethyl ester 
• 66985-46-4 (+/-)-2-(4-chlorophenyl)-2-(trimethylsiloxy)-acetonitrile 
• 34966-48-8 ethyl 2-(4-chlorophenyl)-2-oxoacetate 
• 924-44-7 glyoxylic acid ethyl ester 
• 1679-18-1 4-Chlorophenylboronic acid 
• 104-88-1 4-chlorobenzaldehyde 

Downstream Products

• 5445-25-0 ethyl 2-bromo-2-(4-chlorophenyl)acetate 
• 74569-27-0 Ethyl 4-chloro-α-fluorophenylacetate 
• 2819-63-8 chloro-(4-chloro-phenyl)-acetic acid ethyl ester 
• 67593-06-0 2-(5-Chloro-2-ethoxycarbonylmethyl-phenyl)-propionic acid ethyl ester 
• 853680-28-1 2-(4-chlorophenyl)-2-fluoro-pentanedioic acid 1-ethyl ester 
• 34966-48-8 ethyl 2-(4-chlorophenyl)-2-oxoacetate 

Relevant academic research and scientific papers

Hydroacylation of activated ketones catalyzed by N-heterocyclic carbenes

N-heterocyclic carbenes derived from triazolium salts are effective catalysts between 10 and 15 mol % for the hydroacylation of activated ketones. The reducing equivalent is generated via the interaction of a nucleophilic carbene species and an aromatic aldehyde. The subsequent alcohol product can undergo an acylation event with the resulting acyl heteroazolium intermediate formed in situ between the NHC and the aldehyde. This unprecedented multiple bond-forming reaction can accommodate aromatic aldehydes as the hydride source and various electron-deficient ketones. Preliminary mechanistic evidence indicates that the reduction and acylation steps are sequential operations. The intramolecular variant of this organocatalytic reaction affords benzofuranones in good yield. Copyright

Tunable System for Electrochemical Reduction of Ketones and Phthalimides

Herein, we report an efficient, tunable system for electrochemical reduction of ketones and phthalimides at room temperature without the need for stoichiometric external reductants. By utilizing NaN3 as the electrolyte and graphite felt as both the cathode and the anode, we were able to selectively reduce the carbonyl groups of the substrates to alcohols, pinacols, or methylene groups by judiciously choosing the solvent and an acidic additive. The reaction conditions were compatible with a diverse array of functional groups, and phthalimides could undergo one-pot reductive cyclization to afford products with indolizidine scaffolds. Mechanistic studies showed that the reactions involved electron, proton, and hydrogen atom transfers. Importantly, an N3/HN3 cycle operated as a hydrogen atom shuttle, which was critical for reduction of the carbonyl groups to methylene groups.

Biocatalysed reductions of α-ketoesters employing CyreneTM as cosolvent

The search for novel reaction media with environmental friendly properties is an area of great interest in enzyme catalysis. Water is the medium of biocatalysed processes, but due to its properties, sometimes the presence of organic (co)solvents is required. CyreneTM represents one of the newest approaches to this medium engineering. This polar solvent has been employed for the first time in biocatalysed reductions employing purified alcohol dehydrogenases. A set of α-ketoesters has been reduced to the corresponding chiral α-hydroxyesters with high conversions and optical purities, being possible to obtain good results at Cyrene contents of 30% v/v and working at substrate concentrations of 1.0 M in presence of 2.5% v/v of this solvent. At this concentration, the presence of Cyrene has a beneficial effect in the bioreduction conversion.

Exploiting Cofactor Versatility to Convert a FAD-Dependent Baeyer–Villiger Monooxygenase into a Ketoreductase

Cyclohexanone monooxygenases (CHMOs) show very high catalytic specificity for natural Baeyer–Villiger (BV) reactions and promiscuous reduction reactions have not been reported to date. Wild-type CHMO from Acinetobacter sp. NCIMB 9871 was found to possess an innate, promiscuous ability to reduce an aromatic α-keto ester, but with poor yield and stereoselectivity. Structure-guided, site-directed mutagenesis drastically improved the catalytic carbonyl-reduction activity (yield up to 99 %) and stereoselectivity (ee up to 99 %), thereby converting this CHMO into a ketoreductase, which can reduce a range of differently substituted aromatic α-keto esters. The improved, promiscuous reduction activity of the mutant enzyme in comparison to the wild-type enzyme results from a decrease in the distance between the carbonyl moiety of the substrate and the hydrogen atom on N5 of the reduced flavin adenine dinucleotide (FAD) cofactor, as confirmed using docking and molecular dynamics simulations.

Boron-Catalyzed O-H Bond Insertion of α-Aryl α-Diazoesters in Water

A catalytic, metal-free O-H bond insertion of α-diazoesters in water in the presence of B(C6F5)3·nH2O (2 mol %) was developed, affording a series of α-hydroxyesters in good to excellent yields. The reaction features easy operation and wide substrate scope, and importantly, no metal is needed as compared with the conventional methods. Significantly, this approach further expands the applications of B(C6F5)3 under water-tolerant conditions.

Asymmetric catalytic arylation of ethyl glyoxylate using organoboron reagents and Rh(i)-phosphane and phosphane-phosphite catalysts

Herein we report the first application of Rh(i)-phosphane and phosphane-phosphite catalysts in the enantioselective catalytic arylation of ethyl glyoxylate with organoboron reagents, providing access to ethyl mandelate derivatives in high yield (up to 99%) and moderate to very good enantioselectivities (up to 75% ee). Commercial phosphane ligands, such as (R)-MonoPhos and (R)-Phanephos were tested, as well as non-commercial (R,R)-TADDOL-derived phosphane-phosphite ligands. Those ligands containing bulky substituents in the ortho-and para-positions of the chiral phosphite moiety were found to be the most selective.

Iron-catalyzed hydrogenation for the in situ regeneration of an NAD(P)H model: Biomimetic reduction of α-Keto-/α-iminoesters

Two irons for a smoother finish: An NAD(P)H model was regenerated readily in situ by iron-catalyzed reduction with molecular hydrogen. The subsequent biomimetic reduction of α-keto-/ α-iminoesters proceeded smoothly in the presence of an iron-based Lewis acid (LA) to provide α-hydroxyesters and amino acid esters in good to excellent yields (see scheme; NAD(P) +=nicotinamide adenine dinucleotide (phosphate), TM=transition metal). Copyright

Expeditious and novel synthesis of α-hydroxyesters via rhodium-NHC catalyzed arylation of ethyl glyoxalate

The rhodium-NHC catalyzed arylation reaction of ethyl glyoxalate with aryl and alkyl boronic acids provides an efficient method for the synthesis of α-hydroxyesters. A wide range of α-hydroxyesters (up to 12) were prepared in good to excellent yields. KOtBu was the base of choice, along with tert-amyl alcohol as the solvent. As far as we are aware, this is the first report of this catalytic arylation, using rhodium-NHC catalysts with this specific substrate type.

Suzuki-Miyaura coupling reaction of boronic acids and ethyl glyoxylate: Synthetic access to mandelate derivatives

The palladium-catalyzed coupling reaction of arylboronic acids with ethyl glyoxylate provides a straightforward method for the synthesis of mandelic esters. Pd2(dba)3·CHCl3 in combination with 2-di-tert-butylphosphanylbiphenyl as the catalytic system and Cs 2CO3 as the base were used. The reaction tolerates a wide range of functionalized boronic acids. Mandelic esters were isolated in good-to-excellent yields with a variety of neutral, slightly electron-rich, and slightly electron-poor substituents. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Reduction of activated carbonyl groups by alkyl phosphines: Formation of α-hydroxy esters and ketones

Reduction of activated carbonyl groups such as α-keto esters, benzils, 1,2-cyclohexanedione, and α-ketophosphonates by alkyl phosphines afforded the corresponding α-hydroxy esters or ketones in good to excellent yields in THF at room temperature. The mechanism of the proton transfer and intramolecular hydrolysis has been studied on the basis of deuterium and 18O labeling experiments. The Royal Society of Chemistry 2006.