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

David M. Hodgson | Zendy; Stanislav Man | Zendy; Kimberley Jade Powell | Zendy; Ziga Perko | Zendy; Minxiang Zeng | Zendy; Elena MorenoClavijo | Zendy; Amber L. Thompson | Zendy; Michael Moore | Zendy

Open Access

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

Author(s) -

David M. Hodgson,

Stanislav Man,

Kimberley Jade Powell,

Ziga Perko,

Minxiang Zeng,

Elena MorenoClavijo,

Amber L. Thompson,

Michael Moore

Publication year - 2014

Publication title -

the journal of organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.2

H-Index - 228

eISSN - 1520-6904

pISSN - 0022-3263

DOI - 10.1021/jo501893r

Subject(s) - oxonium ion , ylide , chemistry , sigmatropic reaction , acetal , stereocenter , intramolecular force , stereochemistry , diazo , intramolecular reaction , medicinal chemistry , enantioselective synthesis , catalysis , organic chemistry , ion

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.

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