Density Functional Theory Study of the Cinchona Thiourea‐ Catalyzed Henry Reaction: Mechanism and Enantioselectivity

We report a density functional theory investigation of the enantioselective Cinchona thiourea‐catalyzed Henry reaction of aromatic aldehydes with nitromethane. We show that two pathways (differing in the binding modes of the reactants to the catalyst) are possible for the formation of the CC bond, and that they have comparable reaction barriers. The enantioselectivity is investigated, and our results are in agreement with the experimentally observed solvent dependence of the reaction.