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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.

Original publication

DOI

10.1021/jo501893r

Type

Journal article

Journal

J Org Chem

Publication Date

17/10/2014

Volume

79

Pages

9728 - 9734

Keywords

Acetals, Furans, Molecular Structure, Onium Compounds, Rhodium, Spiro Compounds, Stereoisomerism