66693-08-1

Upstream product

• 108-86-1 bromobenzene 
• 7605-30-3 ethyl 2-phenylsulfonylacetate 
• 134919-31-6 ethyl α-diazo-α-phenylsulfonylacetate 
• 71-43-2 benzene 
• 2882-19-1 ethyl 2-phenyl-2-bromoacetate 
• 108-98-5 thiophenol 
• 873-55-2 sodium benzenesulfonate 

Downstream Products

• 1603-79-8 phenylglyoxylic acid ethyl ester 
• 51416-86-5 α-benzenesulfonyl-α-phenylpropionic acid 
• 24422-78-4 phenyl α-methylbenzyl sulfone 
• 190672-20-9 ethyl 2-(methylthio)-2-phenyl-2-(phenylsulfonyl)acetate 
• 66693-09-2 Ethyl-α-benzolsulfonyl-α-phenylpropionat 

Relevant academic research and scientific papers

Palladium-catalyzed Negishi α-arylation of alkylsulfones

A general, mild catalytic system for α-monoarylation of various alkyl sulfones is described that utilizes palladium-catalyzed Negishi cross-coupling approach.

Selective sulfenylative desulfonylation or decarbalkoxylation of α-sulfonyl malonates with DABCO or Bu3N: Reactivity and conformational analysis

The study on reactivity of severalαsubstituted αsulfonyl malonates toward 1,4-diazabicyclo[2.2.2]octane (DABCO) and Bu3N is described. The reactivity with DABCO revealed the possible competition between decarbalkoxylation and unexpected desulfonylation, depending on the-substituent, because of sterical hindrance around the electrophilic centers (SO2 and CO2R). The derivatives with crowded α-substituents suffer selective desulfonylation, and a novel and efficient desulfonylation method can be proposed. The dependence of the reactivity ofα-sulfonyl malonates on the sterical hindrance around the electrophilic centers is confirmed by conformational analysis (Macromodel/MM2* and Mopac/MP3). The carbanionic mechanism is proved because the corresponding protonated, deuterated, and sulfenylated products were obtained by addition of the corresponding electrophilic agents. Bu3N showed itself to be a novel selective decarbalkoxylation agent for any-substituted-sulfonyl malonate.

Formal aromatic C-H insertion for stereoselective isoquinolinone synthesis and studies on mechanistic insights into the C-C bond formation

(Chemical Equation Presented) Formal aromatic C-H insertion of rhodium(II) carbenoid was intensively investigated to develop a new methodology and probe its mechanism. Contrasting with the previously proposed direct C-H insertion, the mechanism was revealed to be electrophilic aromatic substitution, which was supported by substituent effects on the aromatic ring and a secondary deuterium kinetic isotope effect. Various isoquinolinones were synthesized intramolecularly via six-membered ring formation with high regioand diastereoselectivity, while averting the common Buchner-type reaction. Intermolecularly, dirhodium catalyzed formal aromatic C-H insertion on electron-rich aromatics was also achieved.

Palladium-catalyzed arylation of sulfones

A procedure was developed for monoarylation of sulfones with aryl halides in the presence of palladium complexes. Optimal reaction conditions were found, and the scope of application of the proposed procedure was determined. The arylation occurs only with those sulfones which are relatively strong CH acids; the corresponding monoarylated sulfones are formed in moderate to high yields. The arylation of carbanions derived from the sulfones and some other CH acids requires the presence of an additional equivalent of base. The presence of the latter is also necessary in stoichiometric reactions of carbanions with the palladium complex CF3C6H4Pd(PPh3)2Br; no reaction occurs in the absence of a base. A new mechanism of arylation was proposed, where the key stage is deprotonation of palladium intermediate ArPdL2CHXY which activates the reductive elimination stage.

Palladium-catalyzed arylation of sulfonyl CH-acids

A method for the palladium-catalyzed monoarylation of a series of functionalized sulfones by aryl halides is described. The reaction proceeds in the presence of 2 mol% of Pd2dba3·CHCl3 (dba=dibenzylideneacetone), PPh3 and NaH as a base, only with relatively strong CH-acids and gives monoarylated products in moderate to high yields.

A novel and easy de-ethoxycarbonylation of α-substituted malonic esters

The reaction of some α-substituted malonic esters with Triton B in DMSO to give the corresponding α-substituted carboxylic esters is reported.

A new methodology for obtaining α-oxo ester equivalents: Sulfanylation of α-sulfonyl carboxylic esters in a solid/liquid phase transfer catalytic system

A new, convenient procedure for the synthesis of a wide range of α-methylsulfanyl-α-phenylsulfonyl carboxylic esters has been developed and their facile conversion to the corresponding α-oxo esters demonstrated.