Department of Chemistry, 207 Pleasant Street, SE, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Org Lett. 2010 Jan 1;12(1):52-5. doi: 10.1021/ol902459z.
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.
（通过双环氧环己烷酮前体的 Wharton 重排得到的）非对映环氧环己烯醇 3a/b 可以通过容易的 vinylogous Payne 重排进行互变。机理问题进行了探讨；双 O-氘代类似物的这种平衡比母体二羟基化合物更慢。在平衡条件下，使用 Amano PS 可以动力学拆分 3a/b 的混合物。这种 DKR 值得注意，因为它在单个事件中设置了四个立体中心。
