60 シス,アンチ,シスートリシクロ[6.3.0.0^<2,6>]ウンデカンの立体制御合成 : (±)-ヒルステンの全合成

概要

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A stereocontrolled synthesis of the illudoid sesquiterpene (±)-hirsutene (3) has been illustrated as an example of a general approach to tricyclic 5-5-5-fused rings: cis,anti,cistricyclo[6.3.0.0^<2,6>]undecanes. Photocycloaddition of the 4-O-acetylcyclohexenone derivative 4 and 2-methylcyclopentane-1,3-dione enol acetate 5 gave the tricyclic 6-4-5-fused ring adduct 6, which was converted to the masked monotosylate 13. Treatment of 13 with potassium carbonate gave the cis,anti,cis-tricyclo-[6.3.0.0^<2,6>]undecane derivative 14 as a result of a unique skeletal-rearrangement. Monoalcohol 20, in turn, was available from 14 in 7 steps, and oxidation of 20 gave the nor-ketone 21, which has previously been converted to hirsutene (3).
天然有機化合物討論会の論文
1979-09-20