The palladium-catalyzed benzylic-like nucleophilic substitution of acetates derived from benzofuran, benzothiophene and indole was investigated. The asymmetric substitution on racemic 1-(2-benzofuryl) ethyl acetate gave disappointing results, but the substitution product was obtained in 98% ee from (S)-1-(2-benzofuryl) ethyl acetate with overall retention of configuration.