5359-49-9

Upstream product

• 15206-55-0 methyl 2-oxo-2-phenylacetate 
• 108-88-3 toluene 
• 73764-13-3 methyl (4-methylphenyl)diazoacetate 
• 71-43-2 benzene 
• 101-41-7 benzeneacetic acid methyl ester 
• 22979-35-7 Methyl phenyldiazoacetate 
• 5720-05-8 4-methylphenylboronic acid 
• 264882-00-0 methyl 2-(2-chlorophenyl)-2-diazoacetate 
• 149-73-5 trimethyl orthoformate 
• 2001-28-7 2-phenyl-1-p-tolyl-ethanone 
• 103-80-0 phenylacetyl chloride 
• 37167-62-7 bromo-phenyl-acetic acid methyl ester 
• 934-56-5 trimethyl(phenyl)stannane 
• 98-80-6 phenylboronic acid 

Relevant academic research and scientific papers

Time-Economical Synthesis of Diarylacetates Enabled by TfOH-Catalyzed Arylation of α-Aryl-α-Diazoesters with Arenes

Diarylacetates are privileged structures of many bioactive natural products and pharmaceutical compounds. A time-economical synthesis of diarylacetates by TfOH-catalyzed arylation of α-aryl-α-diazoesters with arenes is described. This protocol provides a variety of diarylacetates in good yields with broad substrate scope, excellent functional group compatibility, and mild reaction conditions. Also, a new mechanism for the arylation reaction of α-aryl-α-diazoesters with arenes under TfOH catalysis is presented.

Thianthrenation-enabled α-arylation of carbonyl compounds with arenes

The Pd-catalyzed α-arylation of carbonyl compounds with simple arenes enabled by site-selective thianthrenation has been demonstrated. This onepot process using thianthrenium salts as the traceless arylating reagents features mild conditions and a broad substrate scope. In addition, this protocol could also tolerate the heterocyclic carbonyl compounds and complex bioactive molecules, which is appealing for medicinal chemistry.

Room Temperature Coupling of Aryldiazoacetates with Boronic Acids Enhanced by Blue Light Irradiation

A visible-light-promoted photochemical protocol is reported for the coupling of aryldiazoacetates with boronic acids. This photochemical reaction shows great enhancement compared to the same protocol performed in the absence of light. Except for a few cases, the room temperature coupling in the dark (thermal process) generally does not work. When it does, it is likely to also involve free carbenes as key intermediates. Alternatively, photochemical reactions show a broad scope, can be performed under air and tolerate a wide variety of functional groups. Reaction-evolution monitoring, DFT calculations and control experiments have been used to evaluate the main aspects of this intricate mechanistic scenario. Biologically active molecules Adiphenine, Benactyzine and Aprophen have been prepared as examples of synthetic applications.

Gold-catalyzed: Para -selective C-H bond alkylation of benzene derivatives with donor/acceptor-substituted diazo compounds

Herein, we report a gold-catalyzed highly site-selective C(sp2)-H functionalization of unactivated arenes with α-aryl-α-diazoesters with electron-withdrawing substituents as induced groups on aryl rings. Furthermore, the induced groups are useful for further synthetic transformations.

Stereoselective Ketone Rearrangements with Hypervalent Iodine Reagents

The first stereoselective version of an iodine(III)-mediated rearrangement of arylketones in the presence of orthoesters is described. The reaction products, α-arylated esters, are very useful intermediates in the synthesis of bioactive compounds such as ibuprofen. With chiral lactic acid-based iodine(III) reagents product selectivities of up to 73 % ee have been achieved.

CYCLIC AMINE DERIVATIVE AND MEDICINAL USE THEREOF

PROBLEM TO BE SOLVED: To provide a novel compound having RORγ antagonist activity, and provide a therapeutic or preventive agent of autoimmune disease and allergic disease based on RORγ function inhibitory action through RORγ antagonist activity. SOLUTION

RhI-Catalyzed Stille-Type Coupling of Diazoesters with Aryl Trimethylstannanes

A RhI-catalyzed cross-coupling of diazoester with arylstannane was developed. This reaction represents the first Stille-type coupling that uses a diazo compound as the coupling partner. The reaction is operationally simple and can be carried out under mild conditions, thus providing an alternative approach for the synthesis of α-aryl esters. RhI-carbene migratory insertion process is suggested to be involved as the key step in this Stille-type coupling.

Rhodium catalyzed arylation of diazo compounds with aryl boronic acids

A general and efficient synthesis of diarylacetate, a diarylmethine derivative, was accomplished through rhodium catalyzed direct arylation of diazo compounds with arylboronic acids. The reaction tolerates various boronic acid derivatives and functional groups. Notably, chemoselective arylation of diazo compounds over other electrophiles were demonstrated. The efficacy of the developed methodology is shown by the expeditious synthesis of the core structure of diclofensine.

Rh(I)-catalyzed cross-coupling of α-diazoesters with arylsiloxanes

An Rh(I)-catalyzed cross-coupling of diazoesters with arylsiloxanes has been successfully achieved. This transformation is a new method for the construction of the C(sp3)-C(sp2) bond, thus providing an alternative synthesis of α-aryl esters. Rh(I)-carbene migratory insertion has been proposed to be involved in this coupling reaction. The reaction represents the first example of utilizing arylsiloxane as the coupling partner in the carbene-involved cross-coupling reactions.

Novel reductive Friedel-Crafts alkylation of aromatics catalyzed by indium compounds: Chemoselective utilization of carbonyl moieties as alkylating reagents

Reductive Friedel-Crafts alkylation of aromatics with ketones or aldehydes was characteristically catalyzed by indium compounds in preference to general catalysts like AlCl3 and BF3, where hydrosilanes would play an important role both as a hydride donor and as a co-catalyst. Chemoselective utilization of ketone moieties as alkylating reagents took place even in the presence of halogen, ester or ether moieties which are very susceptible under traditional Friedel-Crafts conditions. Discussion on a plausible intermediate was carried out by some controlled experiments.