70484-46-7

Upstream product

• 95-49-8 2-methylchlorobenzene 
• 105-53-3 diethyl malonate 
• 95-46-5 2-methylphenyl bromide 
• 609-09-6 Diethyl ketomalonate 
• 615-37-2 ortho-methylphenyl iodide 
• 624-31-7 4-tolyl iodide 
• 37892-24-3 potassium diethyl malonate 
• 623-49-4 ethyl cyanoformate 
• 40291-39-2 ethyl 2-(2-methylphenyl)acetate 
• 105-58-8 Diethyl carbonate 
• 644-36-0 o-methylphenylacetic acid 
• 7294-50-0 tri-o-tolylboroxine 
• 5256-74-6 1,3-diethyl 2-diazopropanedioate 
• 108-88-3 toluene 

Downstream Products

• 203314-21-0 2-(o-methylphenyl)malonic acid 
• 49769-79-1 dimethyl 2-(2-methylphenyl)malonate 
• 129592-98-9 2-amino-2-(o-tolyl)acetic acid 
• 153742-05-3 dimethyl 2-methyl-2-(2-methylphenyl)malonate 

Relevant academic research and scientific papers

A Unified and Desymmetric Approach to Chiral Tertiary Alkyl Halides

Enantioenriched tertiary alkyl halides are prevalent in bioactive molecules and can serve as versatile synthetic intermediates to construct complex structures. While conventional access to these motifs often hinges on stereoselective carbon-halogen or carbon-carbon bond formation reactions, desymmetric approaches using halogenated and prochiral tetrasubstituted carbons are largely elusive in comparison. Here, we report that a suite of dinuclear zinc catalysts with a prolinol- or pipecolinol-derived tetradentate ligand can reductively desymmetrize a large collection of easily available halomalonic esters to α-halo-β-hydroxyesters. These polyfunctionalized tertiary alkyl fluorides, chlorides, and bromides proved to be useful intermediates toward fluorinated drug analogs and polyhalogenated monoterpenes. The facile intramolecular epoxidation of the chiral chloride and bromide products has also enabled expeditious access to natural products containing tertiary alcohol motifs.

Enantioselective Desymmetrization of 2-Aryl-1,3-propanediols by Direct O-Alkylation with a Rationally Designed Chiral Hemiboronic Acid Catalyst That Mitigates Substrate Conformational Poisoning

Enantioselective desymmetrization by direct monofunctionalization of prochiral diols is a powerful strategy to prepare valuable synthetic intermediates in high optical purity. Boron acids can activate diols toward nucleophilic additions; however, the design of stable chiral catalysts remains a challenge and highlights the need to identify new chemotypes for this purpose. Herein, the discovery and optimization of a bench-stable chiral 9-hydroxy-9,10-boroxarophenanthrene catalyst is described and applied in the highly enantioselective desymmetrization of 2-aryl-1,3-diols using benzylic electrophiles under operationally simple, ambient conditions. Nucleophilic activation and discrimination of the enantiotopic hydroxy groups on the diol substrate occurs via a defined chairlike six-membered anionic complex with the hemiboronic heterocycle. The optimal binaphthyl-based catalyst 1g features a large aryloxytrityl group to effectively shield one of the two prochiral hydroxy groups on the diol complex, whereas a strategically placed "methyl blocker"on the boroxarophenanthrene unit mitigates the deleterious effect of a competing conformation of the complexed diol that compromised the overall efficiency of the desymmetrization process. This methodology affords monoalkylated products in enantiomeric ratios equal or over 95:5 for a wide range of 1,3-propanediols with various 2-aryl/heteroaryl groups.

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.

Oxidative Coupling of Aryl Boron Reagents with sp3-Carbon Nucleophiles: the Enolate Chan-Evans-Lam Reaction

Reported is a versatile new oxidative method for the arylation of activated methylene species. Under mild reaction conditions (RT to 40 C), Cu(OTf)2 mediates the selective coupling of functionalized aryl boron species with a variety of stabilized sp3-nucl

Oxidative coupling of aryl boron reagents with sp3-carbon nucleophiles: The enolate chan–evans–lam reaction

Reported is a versatile new oxidative method for the arylation of activated methylene species. Under mild reaction conditions (RT to 40°C), Cu(OTf)2mediates the selective coupling of functionalized aryl boron species with a variety of stabilized sp3-nucleophiles. Tertiary malonates and amido esters can be employed as substrates to generate quaternary centers. Complementing either traditional cross-coupling or SNAr protocols, the transformation is chemoselective in the presence of halogen electrophiles, including aryl bromides and iodides. Substrates bearing amide, sulfonyl, and phosphonyl groups, which are not amenable to coupling under mild Hurtley-type conditions, are suitable reaction partners.

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.

Catalytic Enantioselective Synthesis of Atropisomeric Biaryls: A Cation-Directed Nucleophilic Aromatic Substitution Reaction

A catalytic enantioselective nucleophilic aromatic substitution reaction which yields axially chiral biaryl derivatives in excellent yields with e.r. values of up to 97:3 has been developed. This process uses a chiral counterion to direct the addition of thiophenolate to a prochiral dichloropyrimidine by a tandem desymmetrization/kinetic resolution mechanism. The products can be derivatized to a range of atropisomeric structures without any reduction in enantioenrichment, thus offering access to unexplored chiral biaryl architectures.

New efficient ligand-free, copper nanoparticle catalyzed coupling reactions of aryl halides with diethyl malonate to produce α-arylation of malonates

Recently synthesized copper nanoparticles (Cu NP) were used to catalyze coupling of aryl halides with diethyl malonates to produce α-aryl malonates. Synthetic conditions, including solvents, relative amounts of reactants, catalyst, and temperature, etc. h

An efficient method for the preparation of mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate using ethyl-1-imidazole carbamate (EImC)

An efficient method for the synthesis of mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate using ethyl-1-imidazole carbamate (EImC) has been described. Using this method many sterically hindered and highly substituted mono α-aryl derivatives of diethyl malonate and ethyl cyanoacetate were synthesized in high yield.

Copper(I) enolate complexes in α-arylation reactions: Synthesis, reactivity, and mechanism

Copper is all bound up: The copper-catalyzed α-arylation of carbonyl compounds occurs through oxidative addition of iodoarenes to the C-bound Cu I enolate species 1 to form an aryl-CuIII intermediate (see scheme). Computational results provide insight into the origins of the relative reactivity of various CuI enolate complexes in the reactions with iodoarenes. Copyright