Modular, Enantioselective Entry into Polysubstituted Shapeshifting Molecules.

Dynamic, shapeshifting hydrocarbons have emerged as enabling frameworks across drug discovery, materials science, and catalysis. Their employment, however, is often hampered by a lack of efficient synthetic methods for their preparation. Herein, we report a unified, concise, and modular synthesis of enantioenriched shapeshifting hydrocarbons (barbaralones and bullvalones) and multisubstituted bullvalenes, leveraging mild photochemical and base-induced rearrangements.