94204-41-8

Upstream product

• 105337-18-6 ethyl 2-(3,5-dimethylphenyl)acetate 
• 95-92-1 oxalic acid diethyl ester 
• 22445-41-6 3,5-dimethylphenyl iodide 
• 105-53-3 diethyl malonate 
• 556-96-7 5-bromo-1,3-xylene 
• 27129-87-9 3,5-dimethylbenzyl alcohol 
• 2745-54-2 3,5-dimethylbenzyl chloride 
• 39101-54-7 3,5-dimethylphenylacetonitrile 
• 108-69-0 3,5-dimethylaminoaniline 
• 5256-74-6 1,3-diethyl 2-diazopropanedioate 
• 108-38-3 m-xylene 

Downstream Products

• 1447564-99-9 3-(3,5-dimethylphenyl)-4-hydroxy-1-methylquinolin-2(1H)-one 
• 1447565-18-5 1',4,6-trimethyl-2,3-diphenyl-2',4'-dihydro-1'H-spiro[indene-1,3'-quinoline]-2',4'-dione 
• 1447565-41-4 3-(3,5-dimethylphenyl)-1-methyl-5,6-diphenylpyrano[2,3,4-de]quinolin-2(1H)-one 

Relevant academic research and scientific papers

Copper(I)-catalyzed C-C and C-O coupling reactions using hydrazone ligands

Copper-catalyzed C-C coupling reaction of aryl iodides with diethylmalonate in toluene at 90C gave arylated malonates using 5 mol% of CuI with hydrazone 1a as a ligand in good yields under an aerobic atmosphere. We also found CuI/hydrazone 1b in toluene to be an efficient catalytic system for C-O coupling reactions of aryl bromides with phenols to give aryl ethers in good yields at 110C under an aerobic atmosphere.

Protonation and transformations of α-diazo-β-dicarbonyl compounds in superacids: generation of the strongest carbon-centered cationic electrophiles at the protonation of diazomalonates in Friedel–Crafts reactions

Protonation of diazodiketones N2C(COR)2in Br?nsted superacids (TfOH, FSO3H, TfOH–SbF5) gives rise to stable and non-reactive O,O-diprotonated at carbonyl oxygens species N2C(C(=OH+)R)2, which were studied by means of1H and13C NMR. Diazomalonates N2C(CO2Alk)2, contrary to diazodiketones, react with TfOH or HF, releasing nitrogen and producing triflates of oxymalonates TfOCH(CO2Alk)2or fluoromalonates FCH(CO2Alk)2, respectively. Diazoketoesters N2C(COR)(CO2Alk) react in the same way only with TfOH, but not with HF. The reactions of diazomalonates with arenes ArH (benzene, toluene, xylenes) in TfOH solution yield corresponding Friedel–Crafts reaction products ArCH(CO2Alk)2. According to performed DFT calculations, trication+CH(C(=OH+)OMe)2, a possible intermediate, which is derived from protonation of dimethyl diazomalonate, should be the strongest cationic carbon-centered electrophile known up to date.

Arylation of diethyl malonate and ethyl cyanoacetate catalyzed by palladium/di-tert-butylneopentylphosphine

α-Arylated carbonyl derivatives are important structural motifs in many natural products and pharmaceutically active compounds. Although arylation of simple monocarbonyl compounds is a well-established methodology, metal-catalyzed arylation of β-dicarbonyl derivatives is significantly more challenging. The ability of β-dicarbonyl anions to bind to palladium in a κ2-O,O mode, rather than the κ1-C-bound mode required for bond formation, often results in the deactivation of catalyst systems. The C-bound form of the enolate can be favored through the use of sterically demanding ligands. Herein, we report that the sterically demanding di-tert-butylneopentylphosphine (DTBNpP) ligand in combination with Pd(dba)2 provides an effective catalyst for the coupling of aryl bromides and chlorides with diethyl malonate. The Pd/DTBNpP system also catalyzes the coupling of aryl bromides with ethyl cyanoacetate.

Room-temperature copper-catalyzed α-arylation of malonates

An effective method in targeting α-aryl malonates is reported. In the presence of a catalytic amount of 2-picolinic acid and Cul, the coupling of aryl iodides with diethyl malonate proceeds smoothly even at room temperature. The high levels of functional group compatibility and exceptionally mild reaction conditions offer this an attractive protocol in accessing a variety of arylated malonates.

A general and mild copper-catalyzed arylation of diethyl malonate

Chemical equation presented A general method for the synthesis of α-aryl malonates is described. The coupling of an aryl iodide and diethyl malonate in the presence of Cs2CO3 and catalytic amounts of copper(I) iodide and 2-phenylphenol affords the α-aryl malonate in good to excellent yields. The mild reaction conditions and high levels of functional group compatibility make this an attractive synthetic alternative to previous methods.