Theoretical calculations on rhodium(III)-Cp* catalyzed asymmetric transfer hydrogenation of acetophenone using monosulfonamide ligands derived from (1R,2R)-diaminocyclohexane

► The Re and Si asymmetric transfer hydrogenation paths of acetophenone are studied. ► Density functional theory predicts the Si path is favored by ΔEa = 3.9 kcal/mol. ► An attractive interaction CH/π favors the Si pathway.