3516-89-0

Upstream product

• 64-17-5 ethanol 
• 501-89-3 4-(carboxymethyl)benzoic acid 
• 80305-93-7 (4-ethoxycarbonyl-benzyl)-malonic acid diethyl ester 
• 51934-41-9 4-iodobenzoic acid ethyl ester 
• 105-53-3 diethyl malonate 
• 141-97-9 ethyl acetoacetate 
• 26496-94-6 Ethyl 4-(bromomethyl)benzoate 
• 5798-75-4 Ethyl 4-bromobenzoate 
• 586-76-5 4-Bromobenzoic acid 
• 7335-27-5 ethyl 4-chlorobenzoate 
• 4334-88-7 p-ethoxycarbonylphenylboronic acid 
• 105-36-2 ethyl bromoacetate 
• 1528-42-3 ethyl 4-acetylphenylacetate 
• 5764-82-9 bromo(2-ethoxy-2-oxoethyl)zinc 

Downstream Products

• 57269-61-1 4-carboethoxymethylbenzoyl chloride 
• 1324052-36-9 ethyl 4-(7-hydroxy-2-(methoxymethyl)-4-oxo-4H-chromen-3-yl)benzoate 
• 1324054-36-5 ethyl 4-(7-hydroxy-4-oxo-2-(trifluoromethyl)-4H-chromen-3-yl)benzoate 
• 1324052-34-7 ethyl 4-(2-(difluoromethyl)-7-hydroxy-4-oxo-4H-chromen-3-yl)benzoate 
• 1324054-52-5 ethyl 4-(7-hydroxy-4-oxo-4H-chromen-3-yl)benzoate 
• 1324054-54-7 ethyl 4-(2-(2,4-dimethoxyphenyl)-2-oxoethyl)benzoate 
• 1324010-45-8 ethyl 4-(2-(2,4-dihydroxyphenyl)-2-oxoethyl)benzoate 
• 1324052-33-6 4-(2-(difluoromethyl)-7-hydroxy-4-oxo-4H-chromen-3-yl)benzoic acid 
• 67592-99-8 4-(Ethoxycarbonyl-hydroxy-methyl)-benzoic acid ethyl ester 
• 155938-27-5 [4-(5,7-Dimethyl-4-oxo-4H-chromen-2-yl)-phenyl]-acetic acid ethyl ester 
• 155938-24-2 [4-(6-Methyl-4-oxo-4H-chromen-2-yl)-phenyl]-acetic acid ethyl ester 
• 155938-68-4 4'-carboethoxymethylflavone 

Relevant academic research and scientific papers

Coupling of Reformatsky Reagents with Aryl Chlorides Enabled by Ylide-Functionalized Phosphine Ligands

The coupling of aryl chlorides with Reformatsky reagents is a desirable strategy for the construction of α-aryl esters but has so far been substantially limited in the substrate scope due to many challenges posed by various possible side reactions. This limitation has now been overcome by the tailoring of ylide-functionalized phosphines to fit the requirements of Negishi couplings. Record-setting activities were achieved in palladium-catalyzed arylations of organozinc reagents with aryl electrophiles using a cyclohexyl-YPhos ligand bearing an ortho-tolyl-substituent in the backbone. This highly electron-rich, bulky ligand enables the use of aryl chlorides in room temperature couplings of Reformatsky reagents. The reaction scope covers diversely functionalized arylacetic and arylpropionic acid derivatives. Aryl bromides and chlorides can be converted selectively over triflate electrophiles, which permits consecutive coupling strategies.

OXIDATIVE COUPLING OF ARYL BORON REAGENTS WITH SP3-CARBON NUCLEOPHILES, AND AMBIENT DECARBOXYLATIVE ARYLATION OF MALONATE HALF-ESTERS VIA OXIDATIVE CATALYSIS

Described herein are methods of oxidative coupling of aryl boron reagents with sp3-carbon nucleophiles, and ambient decarboxylative arylation of malonate half-esters via oxidative catalysis.

Ambient Decarboxylative Arylation of Malonate Half-Esters via Oxidative Catalysis

We report decarboxylative carbonyl α-arylation by coupling of arylboron nucleophiles with malonic acid derivatives. This process is enabled by the merger of aerobic oxidative Cu catalysis with decarboxylative enolate interception reminiscent of malonyl-CoA reactivity in polyketide biosynthesis. This method enables the synthesis of monoaryl acetate derivatives containing electrophilic functional groups that are incompatible with existing α-arylation reactivity paradigms. The utility of the reaction is demonstrated in drug intermediate synthesis and late-stage functionalization.

Selective synthesis of arylacetic acid esters from ethyl acetoacetate and aryl halides in the presence of copper(II) on 4 ? molecular sieves

A heterogeneous catalyst, copper(II) on 4 ? molecular sieves has successfully been used in the arylation of ethyl acetoacetate, selectively forming arylacetic esters in high yields. The air stable and easily handled catalyst can be simply filtered off during purification thus avoiding significant metal contamination of the product.

PROCESS FOR PREPARING ARYL- AND HETEROARYLACETIC ACID DERIVATIVES

The invention relates to a process for preparing aryl- and heteroarylacetic acids and derivatives thereof by reaction of aryl or heteroaryl halides with malonic diesters in the presence of a palladium catalyst, of one or more bases and optionally of a phase transfer catalyst. This process enables the preparation of a multitude of functionalized aryl- and heteroarylacetic acids and derivatives thereof, especially also the preparation of arylacetic acids with sterically demanding substituents.

Alcohol assisted C-C bond breaking: Copper-catalyzed deacetylative α-arylation of β-keto esters and amides

A method of alcohol-assisted copper-catalyzed highly selective deacetylative α-arylation of β-keto esters and amides has been demonstrated, which illustrated an efficient example of achieving α-aryl esters and amides. From the synthetic point of view, this arylation protocol is general and practical, representing a simple way to produce α-arylated carbonyl compounds from basic starting materials at low cost.

CHROMONE INHIBITORS OF S-NITROSOGLUTATHIONE REDUCTASE

The present invention is directed to inhibitors of S-nitrosoglutathione reductase (GSNOR), pharmaceutical compositions comprising such GSNOR inhibitors, and methods of making and using the same.

Palladium-catalyzed cross-coupling of sterically demanding boronic acids with α-bromocarbonyl compounds

A catalyst system generated in situ from Pd(dba)2 and tri(o-tolyl)phosphine mediates the coupling of arylboronic acids with alkyl α-bromoacetates under formation of arylacetic acid esters at unprecedented low loadings. The new protocol, which involves potassium fluoride as the base and catalytic amounts of benzyltriethylammonium bromideas a phase transfer catalyst, is uniquely effective for the synthesis of sterically demanding arylacetic acid derivatives. (Figure presented)

Practical synthesis of 2-arylacetic acid esters via palladium-catalyzed dealkoxycarbonylative coupling of malonates with aryl halides

A new palladium-based system was developed that catalyzes the coupling of aryl halides with diethyl malonates in the presence of mild bases. In the course of the reaction, the intermediately formed diethyl arylmalonate is directly converted into the arylacetic acid ester via liberation of carbon dioxide and an alkanol. This cross-coupling/dealkoxycarbonylation process provides an efficient and high-yielding synthetic entry to diversely functionalized arylacetic acid esters. Two complementary protocols were developed, one of which is optimal for electron-rich, the other for electron-poor aryl halides. Both make use of low loadings of palladium(0) bis(dibenzylideneacetone) (0.5 mol%)/tri-tert-butylphosphonium tetrafluoroborate (1.1 mol%) as the catalyst and diethyl malonate as the reaction solvent. The new procedures are particularly effective for sterically hindered substrates. Copyright

Process for Preparing Aryl- and Heteroarylacetic Acid Derivatives

The present invention relates to a novel process for preparing α-arylmethylcarbonyl compound of the formula (III), characterized in that aryl- and heteroarylacetic acids and derivatives thereof of the formula (I) are reacted with α-halomethylcarbonyl compounds of the formula (II) in the presence of a palladium catalyst, of a phosphine ligand, of an inorganic base and of a phase transfer catalyst, optionally using an organic solvent.