Direct catalytic arylation of heteroarenes with meso-bromophenyl-substituted porphyrins
نویسندگان
چکیده
The arylation of mono-, di- and tetra-meso-bromophenyl-substituted porphyrins with the heteroarenes containing "acidic" C-H bonds, such as benzoxazole, benzothiazole and N-methylimidazole was studied in the presence of three alternative catalytic systems: Pd(dba)2/DavePhos/Cs2CO3, Pd(PPh3)4/PivOH/K2CO3 and Pd(OAc)2/Cu(OAc)2/PPh3/K2CO3. The first catalytic system was found to be successful in the reaction with benzoxazole, the second one was less efficient for our purpose, while the third system proved to be most versatile and afforded corresponding mono-, di-, tri- and even tetraarylated derivatives of porphyrins.
منابع مشابه
Palladium-catalyzed amination of meso-(bromophenyl)porphyrins with diamines and azamacrocycles.
Novel diamino and azamacrocycle functionalized porphyrins were efficiently synthesized by palladium-catalyzed amination of mono- and bis(meso-(bromophenyl))porphyrins. The optimization of reaction conditions allowed us to achieve high yields of products with substrates of different types. Supramolecular utility of the thus obtained aminoporphyrins was shown by investigations of processes of coo...
متن کاملOne-Flask Synthesis of Meso-Substituted Dipyrromethanes and Their Application in the Synthesis of Trans-Substituted Porphyrin Building Blocks
The reaction at room temperature of an aldehyde with excess pyrrole in the absence of solvent affords the meso-substituted dipyrromethane. The reaction is catalyzed with trifluoroacetic acid or with BF9,0(Et)2. The dipyrromethaue is purified by crystallixation or by flash chromatography on silica with eluants containing 1% triethylamine. The reaction is compatible with aliphatic or aromatic ald...
متن کاملSynthesis of Asymmetrical Porphyrins Substituted in the meso-Position from Dipyrrolomethanes
A convenient procedure for the synthesis of 5-(4-acetamidophenyl)-10,15,20tris(4-substituted phenyl) porphyrins from dipyrrolomethane is reported. meso-(4Substituted phenyl) dipyrrolomethanes were obtained in yields of 72-84%. The amide porphyrins were isolated with appreciable yields of 15-17%. Introduction The design of new material systems involves the synthesis of asymmetric porphyrins. Thu...
متن کامل5,10-A2B2-type meso-substituted porphyrins--a unique class of porphyrins with a realigned dipole moment.
Current applications in porphyrin chemistry require the use of unsymmetrically substituted porphyrins. Many current industrial interests in optics and biomedicine require systems with either push-pull (electron-donating and -withdrawing groups) or amphiphilic systems (hydrophobic and hydrophilic groups). In this context we present the class of 5,10-A(2)B(2)-type porphyrins for which two differe...
متن کاملPalladium-Catalyzed Direct Arylation of 5-Halouracils and 5-Halouracil Nucleosides with Arenes and Heteroarenes Promoted by TBAF
The 1-N-benzyl-5-iodo(or bromo)uracil undergoes Pd-catalyzed [Pd2(dba)3] direct arylation with benzene and other simple arenes in the presence of TBAF in DMF without the necessity of adding any ligands or additives to give 5-arylated uracil analogues. The TBAF-promoted coupling also occurs efficiently with electron rich heteroarenes at 100 °C (1 h) even with only small excess of heteroarenes. T...
متن کامل