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Synthetic studies directed toward the AB decalin common to HMP-Y1 and hibarimicinone.

ABSTRACT: Efforts toward the synthesis of the decalin ring system common to the hibarimicin shunt metabolite HMP-Y1 and parent aglycone hibarimicinone are reported herein. An intramolecular Diels-Alder cyclization rapidly generated the decalin framework. Two approaches toward completion of the AB decalin were vetted. Incorporation of a phenylsulfonyl leaving group ?- to both a ketone and a ?-lactone followed by base-induced elimination of sulfinate led to the undesired ?,?-unsaturated lactone. Methanolysis of the ?-lactone followed by elimination produced the unexpected bridged cyclic ether by way of an intramolecular oxy-Michael addition of the endo oriented C13 alcohol.

SUBMITTER: Hempel JE

PROVIDER: S-EPMC7449242 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature

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Synthetic studies directed toward the AB decalin common to HMP-Y1 and hibarimicinone.

Hempel Jonathan E JE Engers Darren W DW Sulikowski Gary A GA

Tetrahedron letters 20140226 13

Efforts toward the synthesis of the decalin ring system common to the hibarimicin shunt metabolite HMP-Y1 and parent aglycone hibarimicinone are reported herein. An intramolecular Diels-Alder cyclization rapidly generated the decalin framework. Two approaches toward completion of the AB decalin were vetted. Incorporation of a phenylsulfonyl leaving group β- to both a ketone and a γ-lactone followed by base-induced elimination of sulfinate led to the undesired α,β-unsaturated lactone. Methanolysi ...[more]

PMID: 32855575

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