Solvent‐Regulated Diastereodivergent [3 + 2] Annulations of CF3‐Containing Morita−Baylis−Hillman Carbonates with Cyclic Sulfonimines

Comprehensive Summary A solvent‐regulated diastereodivergent [3 + 2] annulation reaction between Morita‐Baylis‐Hillman carbonates from aryl trifluoromethyl ketones and cyclic sulfonimines is developed under the catalysis of a modified cinchona alkaloid, furnishing diverse polycyclic products bearing vicinal quaternary stereogenic centers with outstanding enantioselectivity and moderate to high diastereoselectivity.