Tobacco Cembranoids

The discovery of the first diterpenoids of the cembrane type in tobacco dates back to the early 1960's. Since then some forty tobacco cembranoids have been encountered. Most of these have a hydroxyl substituent at C-4 and are commonly divided into two series: those having a 4R- and those having a 4S-configuration. Additional oxygenation is found at C-6, C-7, C-8, C-11 or C-12. These compounds, which are present in the gummy exudate of the tobacco leaf and flower, are susceptible to biodegradation thus accounting for the presence of the large number of odoriferous norcembranoids in tobacco. They are also reported to include representatives having growth inhibiting and insect resistance properties. A considerable insight into the biological transformations of the tobacco cembranoids has been obtained by isolation and determination of the stereostructures of new compounds and by biomimetic experiments. The latter have involved singlet oxygen reactions, epoxidations and acid- and base-induced rearrangements. The results obtained support the importance of the (1S,2 E,4R,6R,7E,11 E)- and (1 S,2 E,4 S,6R,7 E,11 E)-2,7,11-cembratriene-4,6-diols, the major tobacco cembranoids, as key metabolites in the biogenesis of the other cembranic compounds. An account of these biogenetic reactions will be given and the isolation of a few new cembranoids will be reported.