Under the conditions of the Wharton reaction, the (±)‐epoxy‐γ‐dihydroionones 2 and 3 are transformed into the allylic alcohols 4–10. γ‐Damascols 4, 5 and 8 were oxidised to cis‐ and trans‐γ‐damascone 12 and 13. Alternatively, dehydro‐γ‐damascol 18 was obtained by Wittig rearrangement of butinyl ether 17, and converted into damascones 12 and 13.
(‐)‐Caryophyllen (1) lagert sich oberhalb 240° in (4S)‐(+)‐4,8,8‐Trimethyl‐4‐vinyl‐bicyclo[5.2.0]non‐2‐en (3) um, das sich über (‐)‐iso‐Caryophyllen (2) mit seinem Diastereomeren 4 ins Gleichgewicht setzt. Die Isomerisierungen erfolgen nach dem Prinzip einer Cope‐Umlagerung.
Diastereoselective Odor Perception of Alcohols in the Ionone Series
The characteristic odor of the diastereoisomers 1 and 2 of 1‐(2,2,6‐trimethylcyclohexyl)‐3‐hexanol is configuration dependent, the trans‐alcohol 1 being identified as the sensorily active component. Structure modification of model 1/2, for example substitution on C(2), C(13), and C(14) (ionon numbering) by CH3 groups, introduction of double bonds in the 3‐ or 4‐position, and isosteric substitution of C(7) by an O‐atom, leads to analogues revealing an unequivocal relation between stereochemistry and odor. The specific odor of alcohol 1 is generally released when all substituents are in an equatorial position; the resulting analogy with the molecular size and shape of odoriferous steroids suggests that the release of the particular scent can be correlated with a steroid‐resembling receptor event.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.