Enantiopure Chiral Phosphines Bearing a Sulfinyl Group and their Application in Catalytic Enantiodivergent Synthesis of Polysubstituted Pyrrolines

In this work, a type of enantiopure chiral phosphines bearing a polar S=O sulfinyl group as the chiral unit in the molecule has been developed, which can be prepared in either enantiomeric form from commercially available materials by a three‐step route. The enantiopure chiral phosphines can catalyse enantiodivergent asymmetric [4+1] annulation reactions of α,β‐unsaturated imines and allylic carbonates, delivering polysubstituted pyrrolines in either enantiomeric form in up to 99% yield and up to 99% ee, and thus empower a method for dual stereo‐controlled synthesis of chiral pyrrolines. This work accordingly unveils a practical and predictable strategy to realize enantiodivergent synthesis.