Enantioselective Construction of Fluorinated Tertiary Stereocenters by Rh-Catalyzed [2 + 2 + 2] Cycloaddition of 1,6-Enynes with α-Fluoroacrylamides

We report the enantioselective construction of fluorinated tertiary stereocenters via [2 + 2 + 2] cycloaddition between 1,6-enynes and α-fluoroacrylamides using a chiral cationic Rh(I) catalyst at room temperature with full retention of the fluorine atom. Coordination of the amide carbonyl to Rh may promote insertion and suppress β-fluoride elimination, enabling efficient formation of fluorinated cyclic products with high enantioselectivity. This strategy provides streamlined access to complex bicyclic systems bearing fluorinated tertiary stereocenters from readily available starting materials.