Fig. 6: Mechanism Study of the Allylic Alkylation Reaction of Ketones.
a Deuterium-labeling experiments. b Transition-state structures of TS2 and TS2′ by DFT. Single-point energies were calculated at the PBE0-D3(BJ)/def2-TZVPP/SMD-(iPrOH) level of theory with structures optimized at the B3LYP-D3(BJ)/SDD(Ni)+6−31 G(d)/SMD-(iPrOH) level. The ligand used for the calculations is L6. c Steric map of the catalyst Ni(II)/L6 on the basis of the DFT-optimized structure of TS2. The steric map is viewed down the z-axis; the orientation of the catalyst Ni(II)/L6 is the same as TS2. The red and blue zones indicate the more-hindered and less-hindered zones in the catalytic pocket, respectively. %VBur, percentage of buried volume. d The ratio of two kinds of enolates (Ea) and (Eb) of 2-butanone was calculated under the Boltzmann distribution assumption.
