Reducing properties of 1,2-dipyridyl-1,2-disodioethanes: Chemical validation of theoretical and electrochemical predictions

Azzena, U.;Carraro, M.;Pisano, L.;MOCCI, FRANCESCA;Antonello, S.;Maran, F.

2016-01-01

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Abstract

The reducing properties of highly delocalized radical anions and dianions of 1,2-di(hetero)arylethenes were investigated by theoretical calculations at the PBE0/6-311+G(d,p)/IEFPCM level. The results correlated nicely with the reduction potentials determined by analysis of the voltammetric curves for the reduction of the parent alkenes, and this allowed a reliable scale for their relative reducing strength to be established. In full agreement with calculations and electrochemical results, use of the appropriate 1,2-dipyridyl-1,2-disodioethane as a base led to the successful α-alkylation of bromophenylacetic acids under mild reaction conditions, thus avoiding the competitive reductive cleavage of aromatic C-Br bonds.