Abstract
Superposition analysis of (-)-patchoulol (1 ) and the spirocyclic patchouli odorant
(5R *,6S *)-1,1,6-trimethylspiro[4.5]decan-6-ol
(3 ) suggested the intersection structure
(4aS *,8aS *)-1,1,8a-trimethyldecahydronaphthalen-4a-ol
(4 ) as potential patchouli odorant. The
synthesis commenced with the Robinson annulation of mesityl oxide
with 2-cyanocyclohexanone, accessible by intramolecular cyclization
of pimelonitrile. Weitz-Scheffer epoxidation of the resulting
Michael system with hydrogen peroxide in the presence of sodium
hydroxide and subsequent Wharton rearrangement employing hydrazine
hydrate and acetic acid furnished with complete cis -selectivity
(4aR *,8aR *)- 8a-hydroxy-5,5-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalene-4a-carbonitrile (14 ), possibly
due to neighboring group participation of the cyano function in
the epoxidation step. Subsequent hydrogenation of the allylic double
bond with palladium on carbon as catalyst, followed by reduction
of the nitrile group with DIBAL-H afforded (4aR *,8aR *)- 8a-(aminomethyl)-1,1-dimethyldecahydronaphthalen-4a-ol
(16 ), which was deaminated with hydroxylamine-O -sulfonic acid to afford the target
compound 4 that possesses an interesting
woody odor with green-mossy, camphoraceous, and patchouli-type facets.
Key words
annulations -
cis -decalins - epoxidations - neighboring group effects - odorants
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