Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

Abstract

Abstract:A unique route to the synthesis of 2-alkyl-2-arylphenylsulphonylacetonitriles via the nucleophilic aromatic substitution (SNAr) of chloroarene cyclopentadienyliron complexes with 2-alkyl phenylsulphonylacetonitriles has been investigated. Reactions of chloroarene complexes (la-6) with 2-alkyl phenylsulphonylacetonitrile (2a,b) in the presence of K,CO, in DMF at room temperature led to the formation of complexes 3a-d and 4a,c,d in good yields. The use of alkylated phenylsulphonylacetonitriles as nucleophiles in the reactions with thep-dichlorobenzene complex ( l e ) allowed the formation of the disubstituted complexes (5,6). Photolytic demetallation provided an efficient route to the liberation of the arylated phenylsulphonylacetonitriles 7a-d, 8a,c,d, 9, and 10.Key words: chloroarene, phenylsulphonylacetonitrile, nucleophilic substitution.RCsumC : On explore une mtthode originale de synthbse des 2-alkyl-2-arylphCnylsulphonylacCtonitriles via la substitution aromatique nuclCophile (SNAr) des complexes du chloroarbnecyclopentadiCnyl de fer avec les 2-alkylphCnylsulphonylacCtonitriles. Les rkactions des complexes de choroarbnes (10-6) avec le 2-alkylphCnylsulphonylacCtonitrile (2a,b) en presence de K,CO, dans le DMF a la temperature ambiante conduisent, avec de bons rendements, ? i la formation des complexes 3a-d et 4a,c,d. L'emploi des phCnylsulphonylacCtonitriles alkyICs comme nuclCophiles dans la reaction avec le complexe de p-dichlorobenzbne ( l e ) permet la formation de complexes disubstituCs ( 5 , 6 ) . La dCmCtallation photolytique foumit une excellente voie d'acces a la liberation des phCnylsulphonylacCtonitriles 7a-d, 8a,c,d, 9 et 10.

Radical Perfluoroalkylation of Arenes via Carbanion Intermediates

“…Substrates 5 , S1 ( 12f precursor), S2 ( 12l precursor), and S3 ( 12e precursor) were purchased from commercial suppliers. Aryl substrates S4 ( 12g precursor) and S5 ( 12h precursor) were synthesized according to the literature procedure, and all analytical data were in agreement with the previous reports . Tetralone ester S6 ( 12m precursor) was synthesized according to the literature procedure, and all analytical data were in agreement .…”

Multistate-Mediated Rearrangements and FeCl2 Elimination in Dinuclear FePd Complexes

“…[η 5 -CpFe­(η 6 -C 6 H 5 Cl)] + and ortho -, meta -, para -substituted [η 5 -CpFe­(η 6 -C 6 H 4 Cl 2 )] + are accessible from ferrocene by AlCl 3 -promoted reactions with the corresponding chloro benzene derivative in reasonable yields . Although many compounds have been generated from these precursors by S N Ar reactions, − to the best of our knowledge, no ligand with a [η 5 -CpFe­(η 6 -arene)] + motif linked to a donor site has been described up to now.…”