On the Crossroad of Dienone Musks and Cassyrane: Synthesis and Olfactory Properties of New High-Impact Orris Odorants

Abstract

While investigating the effect of the Cassyrane (rac-3/4) substitution pattern on the odor of dienones, (3E,5E)-5-tert-butylocta­-3,5-dien-2-one (34) was discovered as an orris odorant with the lowest threshold reported so far in the ionone family (0.036 ng/L air). Derivatives 35–37, which allowed some insight into the underlying structure–odor relationships, were synthesized by a sequence consisting of copper(I)-catalyzed Grignard reactions with acyl chlorides, cerium- and lanthanum-assisted Grignard reactions of the resulting products with the Grignard reagent 17, prepared from but-3-yn-2-ol, manganese(IV) oxide oxidation of the secondary hydroxy function, elimination of the tertiary hydroxy function via its mesylate, alanate reduction of the ynone moiety to the corresponding allylic alcohol, and concluding manganese(IV) oxide oxidation. Furthermore, the γ,δ-unsaturated 38–41, and the fully hydrogenated analogues 42–45 were synthesized, and evaluated for their olfactory properties.

Key words

alkynes - dienones - elimination - Grignard reaction - odorants

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