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Dynamic kinetic resolution during a vinylogous Payne rearrangement: a concise synthesis of the polar pharmacophoric subunit of (+)-scyphostatin.

ABSTRACT: The diastereomeric epoxycyclohexenols 3a/b (obtained via a Wharton rearrangement of a bis-epoxycyclohexanone precursor) were shown to undergo interconversion via a facile vinylogous Payne rearrangement. Mechanistic issues were probed; the doubly O-deuterated analogues underwent this equilibration more slowly than the parent dihydroxy compounds. It was possible to kinetically resolve the mixture of 3a/b under equilibrating conditions by use of Amano PS. This DKR is additionally noteworthy because it sets four stereocenters in a single event.

SUBMITTER: Hoye TR

PROVIDER: S-EPMC2804749 | biostudies-literature | 2010 Jan

REPOSITORIES: biostudies-literature

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Dynamic kinetic resolution during a vinylogous Payne rearrangement: a concise synthesis of the polar pharmacophoric subunit of (+)-scyphostatin.

Hoye Thomas R TR Jeffrey Christopher S CS Nelson Dorian P DP

Organic letters 20100101 1

The diastereomeric epoxycyclohexenols 3a/b (obtained via a Wharton rearrangement of a bis-epoxycyclohexanone precursor) were shown to undergo interconversion via a facile vinylogous Payne rearrangement. Mechanistic issues were probed; the doubly O-deuterated analogues underwent this equilibration more slowly than the parent dihydroxy compounds. It was possible to kinetically resolve the mixture of 3a/b under equilibrating conditions by use of Amano PS. This DKR is additionally noteworthy because ...[more]

PMID: 19968321

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