Deprotonative Metalation of Chlorothiophene with Grignard Reagents and Catalytic cis-2,6-Dimethylpiperidine under Mild Conditions

Atsunori Mori, Shunsuke Tamba, Kenji Ide, Keisuke Shono, Atsushi Sugie
2013 Synlett : Accounts and Rapid Communications in Synthetic Organic Chemistry  
Deprotonative metalation of chlorothiophene takes place with a catalytic amount of cis-2,6-dimethylpiperidine (DMP) and an alkyl Grignard reagent at room temperature for 3 h to give the corresponding thienyl Grignard reagent. Polymerization leading to head-to-tail-type poly(3-substituted thiophene) with the thus metalated chlorothiophene proceeds in the presence of a nickel catalyst bearing N-heterocyclic carbene (NHC) ligand. Palladium catalyzed cross-coupling reaction with aryl bromides also
more » ... aryl bromides also gives arylated thiophenes in good to excellent yields whereas the C-Cl bond being intact.
doi:10.1055/s-0033-1338385 fatcat:hyagjqsbivg35ctkuvo7xdueaq