Download PDF
Synthesis 2009(1): 62-68  
DOI: 10.1055/s-0028-1083269
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis and Olfactory Evaluation of (4aR*,8aR*)-1,1,8a-Trimethyl­decahydronaphthalen-4a-ol: A cis-Decalol Intersection Structure of (-)-Patchoulol and (5R*,6S*)-1,1,6-Trimethylspiro[4.5]decan-6-ol

Astrid Jahnkea, Christian Burschkaa, Reinhold Tacke*a, Philip Kraft*b
a Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Fax: +49(931)8884609; e-Mail: r.tacke@mail.uni-wuerzburg.de;
b Givaudan Schweiz AG, Fragrance Research, Überlandstrasse 138, 8600 Dübendorf, Switzerland
Fax: +41(44)8242926; e-Mail: philip.kraft@givaudan.com;
Further Information

Publication History

Received 13 August 2008
Publication Date:
12 December 2008 (online)

    Permissions and Reprints All articles of this category

Corrected by:

Synthesis and Olfactory Evaluation of (4aR*,8aR*)-1,1,8a-Trimethyl­-decahydronaphthalen-4a-ol: A cis-Decalol Intersection Structure of (-)-Patchoulol and (5R*,6S*)-1,1,6-Trimethylspiro[4.5]decan-6-olSynthesis 2009; 2009(03): 512-512
DOI: 10.1055/s-0028-1083326

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

    References

  • 1a Kraft P. Chem. Biodivers.  2008,  5:  970 
    Google Scholar
  • 1b Kraft P. In Current Topics in Flavor and Fragrance Research   Kraft P. Swift KAD. Verlag Helvetica Chimica Acta; Zürich: Wiley-VCH: Weinheim, 2008.  p.133 
    Google Scholar
  • 2 Kraft P. Eichenberger W. Frech D. Eur. J. Org. Chem.  2005,  3233 
    CrossrefGoogle Scholar
  • 3a Fráter G. Bajgrowicz JA. Kraft P. Tetrahedron  1998,  54:  7633 
    Google Scholar
  • 3b Weyerstahl P. J. Prakt. Chem.  1994,  336:  95 
    Google Scholar
  • 4 Kraft P. Weymuth C. Nussbaumer C. Eur. J. Org. Chem.  2006,  1403 
    CrossrefGoogle Scholar
  • 5 Spreitzer H. Helv. Chim. Acta  1990,  73:  1730 
    CrossrefGoogle Scholar
  • 6 Kraft P. Bruneau A. Eur. J. Org. Chem.  2007,  2257 
    CrossrefGoogle Scholar
  • 8 Spreizer H. Monatsh. Chem.  1992,  123:  587 
    CrossrefGoogle Scholar
  • 9 Weyerstahl P. Splittgerber H.-D. Walteich J. Wollny T. J. Essent. Oil Res.  1989,  1:  1 
    CrossrefGoogle Scholar
  • 10 Kaiser R. Meaningful Scents Around the World - Olfactory, Chemical, Biological, and Cultural Considerations   Verlag Helvetica Chimica Acta; Zürich: Wiley-VCH: Weinheim, 2006.  p.152 
    Google Scholar
  • 11 Marshall JA. Hochstetler AR. J. Org. Chem.  1968,  33:  2593 
    CrossrefGoogle Scholar
  • 12 Ohloff G. In Gustation and Olfaction   Ohloff G. Thomas AF. Academic Press; New York: 1971.  p.178 
    Google Scholar
  • 13a Tai C.-L. Ly TW. Wu J.-D. Shia K.-S. Liu H.-J. Synlett  2001,  214 
    Google Scholar
  • 13b Liu H.-J. Ly TW. Tai C.-L. Wu J.-D. Liang J.-K. Guo J.-C. Tseng N.-W. Shia K.-S. Tetrahedron  2003,  59:  1209 
    Google Scholar
  • 14 Weitz E. Scheffer A. Ber. Dtsch. Chem. Ges.  1921,  54:  2327 
    CrossrefGoogle Scholar
  • 15a Payne GB. Williams PH. J. Org. Chem.  1961,  26:  651 
    Google Scholar
  • 15b Sugiyama S. Ôhigashi S. Sawa R. Hayashi H. Bull. Chem. Soc. Jpn.  1989,  62:  3202 
    Google Scholar
  • 16a Trost BM. Salzmann TN. J. Chem. Soc., Chem. Commun.  1975,  571 
    Google Scholar
  • 16b Trost BM. Bogdanowicz MJ. Frazee WJ. Salzmann TN. J. Am. Chem. Soc.  1978,  100:  5512 
    Google Scholar
  • 17a Adam W. Kilic H. Saha-Möller CR. Synlett  2002,  510 
    Google Scholar
  • 17b Zilbeyaz K. Sahin E. Kilic H. Tetrahedron: Asymmetry  2007,  18:  791 
    Google Scholar
  • 18a Ziegler K. Eberle H. Ohlinger H. Liebigs Ann. Chem.  1933,  504:  94 
    Google Scholar
  • 18b Schaefer JP. Bloomfield JJ. Org. React.  1967,  15:  1 
    Google Scholar
  • 19a Ayer WA. Browne LM. Fung S. Can. J. Chem.  1976,  54:  3276 
    Google Scholar
  • 19b Klix RC. Bach RD. J. Org. Chem.  1987,  52:  580 
    Google Scholar
  • 20a Wharton PS. Bohlen DH. J. Org. Chem.  1961,  26:  3615 
    Google Scholar
  • 20b Wharton PS. J. Org. Chem.  1961,  26:  4781 
    Google Scholar
  • 21 Doldouras GA. Kollonitsch J. J. Am. Chem. Soc.  1978,  100:  341 
    CrossrefGoogle Scholar
  • 22 Moretti R. inventors; (Firmenich) PCT Int. Appl. WO  2007135582.  ; Chem. Abstr. 2007, 148, 10969
  • 23a Sheldrick GM. SHELXS-97   University of Göttingen; Germany: 1997. 
    Google Scholar
  • 23b Sheldrick GM. Acta Crystallogr., Sect. A  1990,  46:  467 
    Google Scholar
  • 24 Sheldrick GM. SHELXL-97   University of Göttingen; Germany: 1997. 
    Google Scholar
7

Chemical Computing Group Inc., Molecular Operating Environment MOE 2007.09 software package, Montréal, Québec, Canada H3A 2R7, 2007. For more information, see http://www.chemcomp.com.

25

Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publications no. CCDC-695876 (13) and CCDC-695877 (16). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk].