Stereoselective Total Synthesis of Sesquiterpenoids: (+)-Sativene and (+)-Cyclosativene

References

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• Attempted conversion of keto olefin 5 into diene 7, via other synthetic pathways met with only limited success. For example, we were unable to convert the ketone 5 into the corresponding tosylhydrazone, even under quite drastic conditions15. Furthermore, conversion of ketone 5 into the corresponding enol phosphate, followed by reduction16 of the latter with lithium in ethylamine- t-butyl alcohol under a variety of conditions, failed to produce appreciable quantities of the desired diene 7. Interestingly, the double bond of the vinyl group appeared to be reduced to an appreciable extent under these conditions. We are currently investigating this reaction in greater detail
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• 8 The minor isomer, could also be synthetically utilized. Thus, treatment of 8, with a catalytic amount of p-toluenesulfonic acid in refluxing benzene (30 min.) produced (94%) a mixture of 7 and 8 in a ratio of 7:3
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