Dynamic kinetic resolution during a vinylogous Payne rearrangement: a concise synthesis of the polar pharmacophoric subunit of (+)-scyphostatin.
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.
Hoye
Thomas R
TR
Department of Chemistry, 207 Pleasant Street, SE, University of Minnesota, Minneapolis, Minnesota 55455, USA. hoye@umn.edu
Jeffrey
Christopher S
CS
Nelson
Dorian P
DP
D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D007700:Kinetics; D015394:Molecular Structure; D011753:Pyrones / Q000138:chemical synthesis* / Q000737:chemistry*; D013108:Sphingomyelin Phosphodiesterase / Q000037:antagonists & inhibitors; D013237:Stereoisomerism
D000577:Amides; D011753:Pyrones; C121123:scyphostatin; D013108:Sphingomyelin Phosphodiesterase