Abstract
Thermolysis of 4a (X = H) gives 6a and 6b (X = H) in a ratio of 1∶4 whereas 4b (X = SO2Ph) gives more of the trans-ring junction product 6a (X = SO2Ph) suitable for the synthesis of pisiferol [ratio 6a∶6b (X = SO2Ph) = 1.5∶1]. Base catalysed elimination of the phenylsulfonyl group from 6a (X = SO2Ph) gives 18 which is hydrogenated to 6a (X = H), an intermediate in the synthesis of pisiferol. Both 6a and 6b (X = SO2Ph) have ring B in a half-boat conformation.

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