124493-34-1

Upstream product

• 123726-16-9 bis(4-methylphenyl)iodonium trifluoromethanesulfonate 
• 609-08-5 Diethyl methylmalonate 
• 120976-84-3 phenyl(p-tolyl)iodonium trifluoromethanesulfonate 
• 108-88-3 toluene 
• 624-31-7 4-tolyl iodide 

Relevant academic research and scientific papers

Arylation with unsymmetrical diaryliodonium salts: A chemoselectivity study

Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new "anti-ortho effect" has been identified in the arylation of malonates. Several "dummy groups" have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents. Copyright

Synthesis of 2-Substituted 2-Arylmalonates via Tricarbonylchromium Complexes

Tricarbonylchromium complexes 1 react with monosubstituted malonic acid esters 2 in DMSO at room temperature in the presence of KOtBu to give the complexes 3. After oxidative demetalation, the appropriate aryl derivatives 4 are obtained in moderate to good overall yields. Diastereoselective arylations of chirally modified malonates such as 5a-c were studied. The stereoselectivity was highest for the products 6c/6c′ (80:20) with (-)-8-phenylmenthol as alcohol component in the malonate 5.

Arylation of Diethyl Alkylmalonates: Synthetic Route to Diethyl Alkyl(substituted Aryl)malonates with the Aid of Temporary Arene Complexation by the Cyclopentadienyliron Moiety

Nucleophilic substitution of chlorine in the ironcyclopentadienyl hexafluorophosphates of chlorobenzene, isomeric chlorotoluenes and dichlorobenzenes (1) with the anions generated from diethyl alkylmalonates (2) and (3) leads to the formation of ironcyclopentadienyl complexes of diethyl alkyl(substituted phenyl)malonates (4) and (5).An excess of the anion employed in reactions with the m- and p-dichlorobenzene complexes leads to substitution of both chlorine atoms and formation of isomeric phenylenedimalonate complexes (8).Malonyl cations (4) and (5) possessing a chloro substituent on the complexed phenyl ring provide the possibility of further modifications of phenyl ring substituents via substitution or addition reactions .The described complexes have been demetallated giving diethyl alkyl(substituted phenyl)malonates in >50percent overall yield from the cations (1).All the complexes and compounds have been fully characterized.This approach to the synthesis of the diethyl alkyl(substituted phenyl)malonates which are intermediates in the synthesis of important biologically active barbiturates is easy, efficient, and currently the most general in the area.