Subscribe to RSS
DOI: 10.1055/s-2001-17713
Asymmetric Total Synthesis of a Beer-Aroma Constituent Based on Enantioconvergent Biocatalytic Hydrolysis of Trisubstituted Epoxides
Publication History
Publication Date:
10 August 2004 (online)
![](https://www.thieme-connect.de/media/synthesis/200113/lookinside/thumbnails/10.1055-s-2001-17713-1.jpg)
Abstract
A short asymmetric total synthesis of the plant constituent myrcenediol [(R)-1], and (S)-7,7-dimethyl-6,8-dioxabicyclo[3.2.1]octane (2), which is a volatile constituent of the aroma of beer was accomplished via a chemoenzymatic protocol. The key step consisted of a biocatalytic hydrolysis of trisubstituted epoxides bearing olefinic side chains which proceeded in an enantioconvergent fashion, i.e., a single enantiomeric vic-diol was obtained from the racemate in up to 91% ee and 92% isolated yield.
Key words
epoxide hydrolase - enantioconvergent hydrolysis - trisubstituted epoxide - beer-aroma
- 1
Orru RVA.Faber K. Curr. Opinion Chem. Biol. 1999, 3: 16 - 2
Kroutil W.Mischitz M.Faber K. J. Chem. Soc., Perkin Trans. 1 1997, 3629 - 3
Steinreiber A.Mayer SF.Saf R.Faber K. Tetrahedron: Asymmetry 2001, 12: 1519 - 4
Steinreiber A.Osprian I.Mayer SF.Orru RVA.Faber K. Eur. J. Org. Chem. 2000, 3703 - 5
Osprian I.Stampfer W.Faber K. J. Chem. Soc., Perkin Trans. 1 2000, 3779 - 6
Bohlmann F.Ahmed M.King RM.Robinson H. Phytochemistry 1983, 22: 1281 - 7
Barrero AF.Sanchez JF.Altarejos J.Zafra MJ. Phytochemistry 1992, 31: 1727 - 8
Hioki H.Ooi H.Mimura Y.Yoshio S.Kodama M. Synlett 1998, 729 - 9
Tressl R.Friese L.Fendesack F.Köppler H. J. Agric. Food Chem. 1978, 26: 1422 - 10
Naya Y.Kotake M. Tetrahedron Lett. 1967, 26: 2459 -
11a
Masaki Y.Nagata K.Serizawa Y.Kaji K. Tennen Yuki Kagobutsu Toronkai Koen Yoshishu 1983, 26: 545 - 11b Chem. Abstr. 1983, 101: 23162x
- 12
Ibrahim N.Eggimann T.Dixon EA.Wieser H. Tetrahedron 1990, 46: 1503 - 13
Curran DP.Heffner TA. J. Org. Chem. 1990, 55: 4585 - 14
Crispino GA.Sharpless KB. Synlett 1993, 47 - 16
Hellström H.Steinreiber A.Mayer SF.Faber K. Biotechnol. Lett. 2001, 23: 169 - 17
Yamada S.Oh-hashi N.Achiwa K. Tetrahedron Lett. 1976, 29: 2557 - 18
Yamada S.Oh-hashi N.Achiwa K. Tetrahedron Lett. 1976, 29: 2561 - 19
Kamber M.Pfander H. Helv. Chim. Acta 1984, 67: 968 - 21
Nielsen BE.Lemmich J. Acta Chem. Scand. 1969, 23: 962 - 22
Mischitz M.Kroutil W.Wandel U.Faber K. Tetrahedron: Asymmetry 1995, 6: 1261 - 23
Kroutil W.Osprian I.Mischitz M.Faber K. Synthesis 1997, 156 - 24
Osprian I.Kroutil W.Mischitz M.Faber K. Tetrahedron: Asymmetry 1997, 8: 65 - 25
Krenn W.Osprian I.Kroutil W.Braunegg G.Faber K. Biotechnol. Lett. 1999, 21: 687 - 26
Morizawa Y.Kanakura A.Yamamoto H. Bull. Chem. Soc. Jpn. 1984, 57: 1935 - 27
Vliet MCA.Arends IWCE.Sheldon RA. Synlett 2001, 248 - 28
Fournier-Nguefack C.Lhoste P.Sinou D. Tetrahedron 1997, 53: 4353
References and Notes
Since the biocatalytic hydrolysis of trisubstituted epoxides could proceed in an enantioconvergent fashion (not via kinetic resolution), the general use of E-values for the description of enantioselectivities is inapplicable.
20In contrast, mesylation proceeded very slowly.