W. Fudickar, Katja Vorndran, T. Linker
Nov 13, 2006
Citations
0
Influential Citations
12
Citations
Journal
Tetrahedron
Abstract
Abstract The photooxygenation of homochiral cyclohexene ketals, which are easily available from 2-cyclohexenone and l -tartrates, affords hydroperoxides and after reduction the corresponding allylic alcohols in good yields and high regioselectivities. This can be rationalized by electronic repulsions in a perepoxide intermediate and provides evidence for unfavorable 1,3 diaxial interactions with a dioxolane oxygen atom. Only low stereoselectivities were observed, due to the flexibility of the cyclohexene ring. However, the diastereomers could be separated and after cleavage of the auxiliary, 4-hydroxy-2-cyclohexen-1-one was isolated in enantiomerically pure form, which can serve as a building block for natural product synthesis.