Pleurotus species convert monoterpenes to furanoterpenoids through 1,4-endoperoxides

verfasst von

Sven Krügener, Carmen Schaper, Ulrich Krings, Ralf G. Berger

Abstract

Enzymatic synthesis of furanoterpenoids from β-myrcene and related monoterpenes was observed using a solubilised enzyme fraction of mycelium lyophilisates of several Pleurotus species. The initial enzymatic step, the incorporation of molecular oxygen into the conjugated 1,3-diene moiety, was similar to a 2 + 4 cycloaddition of 1,3-dienes with dienophilic ¹O₂, and was followed by a non-catalysed degradation sequence leading to the furans. The cyclic peroxides 3,6-dihydro-4-(2-(3,3-dimethyloxiran-2-yl)ethyl)-1,2-dioxine and 5-(3,6-dihydro-1,2-dioxin-4-yl)-2-methylpentan-2-ol were identified as key intermediates. Biotransformation of β-myrcene in ¹⁸O-labelled HEPES-buffer did not yield a detectable label in perillene, so a water addition to 3,10-epoxy-β-myrcenes as an alternative was ruled out. The pathway suggested presents a substantiated biogenetic scheme for the formation of monoterpenoid furans and opens biotechnological access to valuable natural flavour compounds, such as perillene and rosefurane. Only one metabolite, identified as the new natural compound 6-methyl-2-methylene-hept-5-enal, carried the ¹⁸O-label. The enzymatic formation of this compound through a 1,2-endoperoxide (3-(5-methyl-1-methylene-hex-4-enyl)-[1,2]-dioxetane) is suggested. The label may simply result from a chemical oxygen exchange between the carbonyl group and the ¹⁸O-labelled water.

Organisationseinheit(en)

Institut für Lebensmittelchemie

Typ

Artikel

Journal

Bioresource technology

Band

100

Seiten

2855-2860

Anzahl der Seiten

6

ISSN

0960-8524

Publikationsdatum

14.02.2009

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.2009.01.001 (Zugang: Unbekannt)