Intramolecular Alkyne-de Mayo Reaction Using the Enol Methylene Acetal Linker: Experimental Implementation and Computational Simulation.

The enol-linked intramolecular alkyne-de Mayo reaction is a photochemically triggered cascade reaction suitable for the synthesis of substituted dihydrotropones by two-carbon ring expansion of enol ethers of cyclopentane-1,3-dion. We report on the implementation of the methylene acetal linker and the isolation of the initial (2 + 2) photocycloadduct in substances. We have investigated in depth the modus operandi of the ring-opening of the π-donor-π-acceptor cyclobutene derivatives by computational chemistry.