Stereodivergent Construction of 1,3‐Chiral Centers via Tandem Asymmetric Conjugate Addition and Allylic Substitution Reaction

Herein, we report a synthesis of cyclohexanones bearing multi‐continuous stereocenters by combining copper‐catalyzed asymmetric conjugate addition of dialkylzinc reagents to cyclic enones with iridium‐catalyzed asymmetric allylic substitution reaction. Good to excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction of adjacent stereocenters (1,2‐position) reported in the literature, the current reaction can achieve the stereodivergent construction of nonadjacent stereocenters (1,3‐position) by a proper combination of two chiral catalysts with different enantiomers. Herein, we report a synthesis of cyclohexanones bearing multi‐continuous stereocenters by combining copper‐catalyzed asymmetric conjugate addition of dialkylzinc reagents to cyclic enones with iridium‐catalyzed asymmetric allylic substitution reaction. Good to excellent yields, diastereoselectivity and enantioselectivity can be obtained. The current reaction can achieve the stereodivergent construction of nonadjacent stereocenters.