Ruthenium hydride-catalyzed regioselective addition of benzaldehyde to dienes leading to β,γ-unsaturated ketones: a DFT study.

Density functional theory (DFT) was used to investigate the ruthenium hydride-catalyzed regioselective addition reactions of benzaldehyde to isoprene leading to the branched β,γ-unsaturated ketone. All intermediates and the transition states were optimized completely at the B3LYP/6-31 G(d,p) level (LANL2DZ(f) for Ru, LANL2DZ(d) for P and Cl). Calculated results indicated that three catalysts RuHCl(CO)(PMe(3))(3) (1), RuH(2)(CO)(PMe(3))(3) (2), and RuHCl(PMe(3))(3) (3) exhibited different catalysis, and the first was the most excellent. The most favorable reaction pathway included the coordination of 1 to the less substituted olefin of isoprene, a hydrogen transfer reaction from ruthenium to the carbon atom C1, the complexation of benzaldehyde to ruthenium, the carbonyl addition, and the hydride elimination reaction. The carbonyl addition was the rate-determining step. The dominant product was the branched β,γ-unsaturated ketone. Furthermore, the presence of one toluene molecule lowered the activation free energy of the transition state of the carbonyl addition by hydrogen bonds between the protons of toluene and the chlorine, carbonyl oxygen of the ruthenium complex. On the whole, the solvent effect decreased the free energies of the species.