A dioxygenase of Pleurotus sapidus transforms (+)-valencene regio-specifically to (+)-nootkatone via a stereo-specific allylic hydroperoxidation

verfasst von

Sven Krügener, Ulrich Krings, Holger Zorn, Ralf G. Berger

Abstract

A selective and highly efficient allylic oxidation of the sesquiterpene (+)-valencene to the grapefruit flavour compound (+)-nootkatone was achieved with lyophilisate of the edible mushroom Pleurotus sapidus. The catalytic reaction sequence was elucidated through the identification of intermediate, (+)-valencene derived hydroperoxides. A specific staining of hydroperoxides allowed the semi-preparative isolation of two secondary (+)-valencene hydroperoxides, 6(R)-Isopropenyl-4(R),4a(S)-dimethyl-2,3,4,4a,5,6,7,8-octahydro-naphthalen-4(S)-yl-hydroperoxide and 6(R)-Isopropenyl-4(R),4a(S)-dimethyl-2,3,4,4a,5,6,7,8-octahydro-naphthalen-2(R)-yl-hydroperoxide. Chemical reduction of the biotransformation products yielded a tertiary alcohol identified as 2(R)-Isopropenyl-8(R),8a(S)-dimethyl-1,3,4,7,8,8a-hexahydro-2H-naphthalen-4a(R)-ol. This suggested a lipoxygenase-type oxidation of (+)-valencene via secondary and tertiary hydroperoxides and confirmed homology data of the key enzyme obtained previously from amino acid sequencing.

Organisationseinheit(en)

Institut für Lebensmittelchemie

Externe Organisation(en)

Justus-Liebig-Universität Gießen

Typ

Artikel

Journal

Bioresource technology

Band

101

Seiten

457-462

Anzahl der Seiten

6

ISSN

0960-8524

Publikationsdatum

17.09.2009

Publikationsstatus

Veröffentlicht

Peer-reviewed

Ja

ASJC Scopus Sachgebiete

Bioengineering, Environmental engineering, Erneuerbare Energien, Nachhaltigkeit und Umwelt, Abfallwirtschaft und -entsorgung

Ziele für nachhaltige Entwicklung

SDG 7 – Erschwingliche und saubere Energie

Elektronische Version(en)

https://doi.org/10.1016/j.biortech.2009.08.087 (Zugang: Unbekannt)