Stereoselectivity in the formation and allylic rearrangement of 8a-methyl- and 8a-ethyl-1,2,3,4,4a,7,8,8a-octahydronaphthalenyl hydroperoxides
作者:David V. Avila、Alwyn G. Davies、Ian G. E. Davison
DOI:10.1039/p29880001847
日期:——
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 °C to give only the 4aβ-alkyl-2,3,4,4a,5,6,7,8,8-octahydronaphthalen-2α-yl hydroperoxides (II). Under the same conditions, the
对4a-甲基-和4a-乙基-1,2,3,4,4a,5,6,7-八氢萘进行了单线态氧氧合,并表征了形成的各种氢过氧化物。证据表明,25°C下8aβ-烷基-1,2,3,4,4a,7,8,8a-八氢萘-4aα-基氢过氧化物(I ; R = Me或Et)在氯仿中不可逆地重排。仅得到4aβ-烷基-2,3,4,4a,5,6,7,8,8-八氢萘-2α-氢过氧化物(II)。在相同条件下,相应的8aβ-烷基-1,2,3,4,4a,7,8,8a-八氢萘-4aβ-基氢过氧化物的重新排列要慢得多。[图形省略]