An intramolecular, stereoselective cyclopropanation of vinylogous carbonates with carbenes using copper catalyst is developed for the synthesis of donor‐acceptor substituted cyclopropapyranones. Completely regioselective ring cleavage of each of the cyclopropane bonds was achieved under suitable reaction conditions, leading to a diverse array of cyclic ethers. The developed method is utilized in the total synthesis of (±)‐diospongin B.

The stereo‐ and regioselective cyclopropanation of vinylogous carbonates utilizes CuI/Cu powder as a catalyst to get access to donor—acceptor substituted cyclopropapyranones.