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

摘要

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.