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.

Development of an Alkyne Analogue of the de†Mayo Reaction: Synthesis of Medium-Sized Carbacycles and Cyclohepta[b]indoles.

Embedded medium-sized carbacycles and cyclohepta[b]indoles occur frequently as scaffold elements in natural products and bioactive compounds. Described herein is a conceptionally novel photochemically triggered cascade process to these scaffolds. Key to the cascading ring-expansion process is an unprecedented intramolecular alkyne analogue of the de Mayo reaction.

Progress toward the Total Synthesis of Gukulenin A: Photochemically Triggered Two-Carbon Ring Expansion Key to α-Tropolonic Ether Synthesis.

The ex-chiral-pool synthesis of an advanced gukulenin A precursor from (-)-piperitone is revealed. Key C/C connecting maneuvers to the synthesis of a C2 dissymmetric bis(α-tropolonic) ether building block are a ring-contracting Meinwald rearrangement, a photochemically triggered two-carbon ring expansion, and a homodimerization by cross-metathesis.