Catalytic Strategies for Diastereodivergent Synthesis

Chiral molecules with multiple stereocenters are widely distributed in nature and drugs. Asymmeric catalysis has allowed the formation of a chiral molecule's enantiomers with equal ease by applying the enantiomeric pair of a chiral catalyst. However, the diastereodivergent synthesis is a great challenge because the formation of one of the diastereomers is inherently preferred in most reactions. Under the efforts of chemists, elegant strategies have been developed to full control of absolute and relative stereochemical configurations. In this Minireview, we highlight the significant advances achieved in this field, and present the diastereo‐control mechanism in the appropriate place on the expectation that new diastereodivergent strategies can be inspired and more types of enantioselective diastereodivergent reactions can be realized. Stereo‐Inspiration: A summary is provided of significant results in the catalytic asymmetric diastereodivergent synthesis without drastically changing the reaction conditions or substrate structures. Diastereocontrol strategies as well as mechanisms are detailed so that they may inspire new diastereodivergent strategies and more types of diastereodivergent reactions.