3062
M. Hall et al. / Tetrahedron: Asymmetry 17 (2006) 3058–3062
6. Wolken, W. A. M.; ten Have, R.; van der Werf, M. J. J.
Agric. Food. Chem. 2000, 48, 5401–5405.
7. Khurana, J. M.; Sharma, P. Bull. Chem. Soc. Jpn. 2004, 77,
549–552.
8. Silva, A. M.; Santos, O. A. A.; Mendes, M. J.; Jordao,
E.; Fraga, M. A. Appl. Catal. A: Gen. 2003, 241, 155–
165.
9. Chen, Y.-Z.; Liaw, B.-J.; Chiang, S.-J. Appl. Catal. A: Gen.
2005, 284, 97–104.
10. Yang, J. W.; Hechavarria Fonseca, M. T.; List, B. Angew.
Chem., Int. Ed. 2004, 43, 6660–6662.
11. Yang, J. W.; Hechavarria Fonseca, M. T.; Vignola, N.; List,
B. Angew. Chem., Int. Ed. 2005, 44, 108–110.
12. Williams, R. E.; Bruce, N. C. Microbiology 2002, 148, 1607–
1614.
13. Steinbacher, S.; Stumpf, M.; Weinkauf, S.; Rohdich, F.;
Bacher, A.; Simon, H. In Flavins and Flavoproteins;
Chapman, S. K., Perham, R. N., Scrutton, N. S., Eds.;
Enoate Reductase Family; Weber: Berlin, 2002; pp 941–
949.
14. Kohli, R. M.; Massey, V. J. Biol. Chem. 1998, 273, 32763–
32770.
15. Shimoda, K.; Ito, D. I.; Izumi, S.; Hirata, T. J. Chem. Soc.,
Perkin Trans. 1 1996, 355–358.
7.68 min, nerol 8.01 min, geraniol 8.38 min, neric and
geranic acid 11.66 and 11.99 min, respectively.
4.4.2. Determination of enantiomeric excess and absolute
configuration. The enantiomeric excess of citronellal and
citronellol was determined using a modified b-cyclodextrin
capillary column (Hydrodex-b-TBDAc, 25 m, 0.25 mm).
Temperature programme for citronellal: 40 °C hold 2 min,
4 °C/min to 120 °C, hold 1 min, 20 °C/min to 180 °C, hold
3 min. Retention times: (S)- and (R)-citronellal 19.84 and
19.97 min, respectively. Temperature programme for
citronellol: 90 °C hold 20 min, 5 °C/min to 160 °C, hold
1 min. Retention times: (S)- and (R)-citronellol 26.17 and
26.33 min, respectively. Sulcatol was analysed after derivat-
isation using acetic anhydride (15 lL) and cat. DMAP with
shaking at room temperature for 5 h. The reaction was
quenched by the addition of H2O (300 lL), EtOAc
(200 lL) was then added and the organic layer was dried
over Na2SO4. Analyses were carried out using a b-cyclo-
dextrin capillary column (CP-Chirasil-DEX CB, 25 m,
0.32 mm, 0.25 lm film). Temperature programme: 80 °C,
hold 10 min, 3 °C/min 180 °C, hold 2 min. Retention times
were as follows: (S)- and (R)-sulcatol (as acetate) 5.18 and
7.09 min, respectively. The absolute configuration of citro-
nellal, citronellol and sulcatol was determined by co-injection
with reference materials of a known absolute configuration.
16. Gatfield, I. L. Adv. Biochem. Eng. Biotechnol. 1997, 55, 221–
238.
17. Ho¨gberg, H.-E.; Berglund, P.; Edlund, H.; Fa¨gerhag, J.;
Hedenstro¨m, E.; Lundh, M.; Nordin, O.; Servi, S.; Vo¨rde, C.
Catal. Today 1994, 22, 591–606.
18. Servi, S. Synthesis 1990, 1–25.
19. Fuganti, C. Pure Appl. Chem. 1990, 62, 1449–1452.
20. Rambeck, B.; Simon, H. Angew. Chem., Int. Ed. Engl. 1974,
13, 609.
Acknowledgement
This study was performed in cooperation with BASF AG
(Ludwigshafen) and financial support is gratefully
acknowledged.
21. Gunther, H.; Simon, H. Biocatal. Biotrans. 1995, 12, 1–26.
¨
22. Simon, H. Indian J. Chem., Sect. B: Org. Chem. Incl. Med.
Chem. 1993, 32B, 170–175.
23. van der Werf, M. J.; Boot, A. M. Microbiology 2000, 146,
1129–1141.
References
24. Muller, A.; Hauer, B.; Rosche, B. J. Mol. Catal. B: Enzym.
¨
2006, 38, 126–130.
25. Brunerie, P.; Brenda, I.; Bock, G.; Schreier, P. Bioconversion
of Monoterpene Alcohols and Citral by Botrytis cinerea. In
Bioflavour ’87; Schreier, P., Ed.; de Gruyter: Berlin, 1988; pp
435–444.
26. Demyttenaere, J. C. R.; De Pooter, H. Phytochemistry 1996,
41, 1079–1082.
27. Devi, J. Rama; Bhattacharyya, P. K. J. Indian Chem. Soc.
1978, 55, 1131–1137.
28. Wolken, W. A. M.; van der Werf, M. J. Appl. Microbiol.
Biotechnol. 2001, 57, 731–737.
1. Somogyi, L. Chem. Ind. 1996, 170–173.
2. Clark, B. C., Jr.; Chamblee, T. S. In Off-Flavors in Food and
Beverages; Charalambous, G., Ed.; Acid-Catalyzed Reactions
of Citrus Oils and Other Terpene Containing Flavors;
Elsevier: Amsterdam, 1992; pp 229–285.
3. Qamar, S.; Hanif, M.; Chaudhary, F. M. Pak. J. Sci. Ind.
Res. 1992, 35, 246–249.
4. Trasarti, A. F.; Marchi, A. J.; Apesteguia, C. R. J. Catal.
2004, 224, 484–488.
5. Ma¨ki-Arvela, P.; Kumar, N.; Kubicka, D.; Nasir, A.;
Heikkila¨, T.; Lehto, V. P.; Sjo¨holm, R.; Salmi, T.; Murzin,
D. Y. J. Mol. Catal. A: Chem. 2005, 240, 72–81.
29. Wolken, W. A. M.; Van Loo, W. J. V.; Tramper, J.; van der
Werf, M. J. Eur. J. Biochem. 2002, 269, 5903–5910.