Intramolecular Oxonium Ylide Formation–[2,3] Sigmatropic Rearrangement of Diazocarbonyl-Substituted Cyclic Unsaturated Acetals: A Formal Synthesis of Hyperolactone C

Rh­(II)-catalyzed oxonium ylide formation–[2,3] sigmatropic rearrangement of α-diazo-β-ketoesters possessing γ-cyclic unsaturated acetal substitution, followed by acid-catalyzed elimination–lactonization, provides a concise approach to 1,7-dioxaspiro­[4.4]­non-2-ene-4,6-diones. The process creates adjacent quaternary stereocenters with full control of the relative stereochemistry. An unsymmetrical monomethylated cyclic unsaturated acetal leads to hyperolactone C, where ylide formation–rearrangement proceeds with high selectivity between subtly nonequivalent acetal oxygen atoms.