Abstract
Spirocyclic analogues of Georgywood® (3) and unlike-10-acetyl-9,10-dimethylbicyclo[6.4.0]dodec-1(8)-ene (4), in which the acetyl moiety and the methyl substituent of C-10 are part of a cyclopentyl
or cyclohexyl ring, were synthesized from 8a-homomyrcene (6) and 4-methylenespiro[2.7]decane (13), respectively. 2-(Dimethylaminomethyl)cyclopentanone (7) or the allyl 1-(acetoxymethyl)-2-oxocycloalkanecarboxylates 14 and 18 were employed as methylene cycloalkanone precursors in an ordinary Diels-Alder reaction
or in [4+2] cycloadditions on the vinyl cyclopropane system 13 in the presence of Wilkinson’s catalyst. By simple LDA-mediated alkylation of the
resulting spirocycles with methyl iodide, further analogues were prepared that provided
additional insight into the structural and stereochemical requirements for the typical
woody-ambery odor character of Iso E Super® (1), and that call a binding model proposed by Hong and Corey into question. The best
odorants found in this study were (1R*,3S*,1′R*)-3,1′,8′,8′-tetramethyl-3′,4′,5′,6′,7′,8′-hexahydro-1′H-spiro[cyclopentane-1,2′-naphthalen]-2-one (10) and (1R*,1′S*,3′S*)-1,3′-dimethyl-3,4,5,6,7,8,9,10-octahydro-1′H-spiro[benzo[8]annulene-2,1′-cyclohexan]-2′-one (17).
Key words
cyclizations - Diels-Alder reactions - Georgywood - odorants - spiro compounds
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