Stereoselectivity in the Formation and Allylic Rearrangement of 8a-Methyl- and 8a-Ethyl-1,2,3,4,4a,7,8,8a-octahydronaphthalenyl Hydroperoxides

Article abstract of DOI:10.1039/P29880001847

4a-Methyl- and 4a-ethyl-1,2,3,4,4a,5,6,7-octahydronaphthalene have been subjected to singlet oxygen oxygenation, and the various hydroperoxides which are formed have been characterised.Evidence is presented that the 8aβ-alkyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-4aα-yl hydroperoxides (I; R=Me or Et) rearrange suprafacially and irreversibly in chloroform at 25 deg C to give only the 4aβ-alkyl-2,3,4,4a,5,6,7,8-octahydronaphthalen-2α-yl hydroperoxides (II).Under the same conditions, the corresponding 8aβ-alkyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-4aβ-yl hydroperoxides rearrange much more slowly.