Enantioselective Synthesis of the Central Ring System of Lomaiviticin A in the Form of an Unusually Stable Cyclic Hydrate

A model system representing a protected form of the four central rings of the antitumor compound lomaiviticin A has been synthesized (outlined in red in the picture). The approach features an intramolecular furan Diels–Alder reaction, a stereoselective oxidative enolate coupling to dimerize the “halves,” and a base‐initiated cascade reaction. The 1,4‐diketone of the central ring system exists as a stable cyclic hydrate.