Chemo-enzymatic Synthesis of (2R,5S)- and (2R,5R)-5-(1-Hydroxy-1-methylethyl)-2-methyl-2-vinyltetrahydrofuran ('Linalool Oxide'): Preparative Application of a Highly Selective Bacterial Epoxide Hydrolase

Synlett

Volumn 1996, Issue 10, 1996, Pages 978-980

  Mischitz, Martin ^a   Faber, Kurt ^a  

^a GRAZ UNIVERSITY OF TECHNOLOGY   (Austria)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002752120     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1996-5638     Document Type: Article

References (21)

1. Wang, D.; Ando, K.; Morita, K.; Kubota, K.; Kobayashi, A. Biosci. Biotech. Biochem. 1994, 58, 2050.
2. Hashimoto, M.; Kan, T.; Yanagiya, M.; Shirahama, H.; Matsumoto, T. Tetrahedron Lett. 1987, 28, 5665.
3. Garcia, M.-A.; Méou, A.; Brun, P. Synlett 1994, 911.
4. Corma, A.; Inglesias, M.; Sánchez, F. J. Chem. Soc., Chem. Commun. 1995, 1635.
5. Méou, A.; Bouanah, N.; Archelas, A.; Zhang, X.M.; Guglielmetti, R.; Furstoss, R. Synthesis 1990, 752.
6. David, L.; Veschambre, H. Tetrahedron Lett. 1984, 25, 543.
7. Mischitz, M.; Kroutil, W.; Wandel, U.; Faber, K. Tetrahedron: Asymmetry 1995, 6, 1261.
8. Mischitz, M.; Faber, K.; Willetts, A. Biotechnol. Lett. 1995, 17, 893.
9. 3 at 0°C. Yield 65% over both steps.
10. The crude enzyme preparation was obtained by hydrophobic interaction chromatography of the cell-free extract according to ref. (8) followed by lyophilization of the active fractions in Trisbuffer. The biocatalyst can be stored for several months at +4°C without loss of activity.
11. 2.
12. 3/MeOH at room temperature is much slower and gives a considerable amount of undesired side product, mainly due to rearrangement of the allylic alcohol moiety. This can completely be suppressed by employing the conditions described.
13. (a) Thomas, A.F.; Thommen, W.; Willhalm, B.; Hagaman, E.W.; Wenkert, E. Helv. Chim. Acta 1974, 57, 2055.
14. (b) Vidari, G.; Giori, A.; Dapiaggi, A.; Lanfranchi, G. Tetrahedron Lett. 1993, 34, 6925.
15. Chen, X.-J.; Archelas, A.; Furstoss, R.; J. Org. Chem. 1993, 58, 5528.
16. Generally, epoxide hydrolases open oxiranes in a trans-specific manner with one oxygen from water being incorporated into the substrate. For a review see: Faber, K.; Mischitz, M.; Kroutil, W. Acta Chem. Scand. 1996, 50, 249.
17. GC/MS-analysis was performed on a HP 6890 GC/MS spectrometer using a HP5-MS column (30m × 0.25mm × 0.25μm film); ionization energy 70eV; program: 80°C, 0min - 10°C/min - 200°C; retention times: (3R,6R)-2 9.38min, (3S,6R)-2 9.42min.
18. (a) Blée, E.; Schuber, F. Eur. J. Biochem. 1995, 230, 229.
19. (b) Bellucci, G.; Chiappe, C.; Cordoni, A. Tetrahedron: Asymmetry 1996, 7, 197.
20. 13mm = 125°C).
21. The slight discrepancy (<5%) betweeen the regioselectivity of the OH-incorporation (GC/MS-analysis) and the observed d.e. of the product (chiral GC) is due to the lower accuracy of the former method.