Theoretical Investigations of Ni/( R , R )‐Me‐DuPhos‐Catalyzed Enantioselective Hydroalkoxylation of 1,3‐Dienes With Methanol

ABSTRACT ( R , R )‐Me‐DuPhos‐nickel‐promoted regioselective and enantioselective intermolecular hydroalkoxylation of linear phenyl diene with methanol was estimated by DFT computation at the ω B97XD/6‐31G(d,p) level (SDD for Ni and Fe). Calculated results elucidated that this hydroalkoxylation occurred through the Ni 0 /Ni II catalytic cycle, involving two important elementary steps: the oxidative additions of methanol and the C–O bond formation. The methanol O–H bond activation included three kinds of reaction channels, and the ligand‐to‐ligand H transfer reaction was the most dominant. Ni‐catalyzed hydroalkoxylation showed complete branched regioselectivity and excellent enantioselectivity. The ligand‐to‐ligand H transfer reaction was the regioselectivity‐limited step, dominantly controlled by both the distortion energy of MeOH and TS interaction energy. The C–O bond formation was the enantioselectivity‐limited step, determined mainly by the distortion energy of the allyl group. Moreover, the role of MeOH, prediction of ligands, and comparison between the inner‐ and outer‐sphere channel were also discussed in detail in this text.