TY - JOUR

T1 - Pleurotus species convert monoterpenes to furanoterpenoids through 1,4-endoperoxides

AU - Krügener, Sven

AU - Schaper, Carmen

AU - Krings, Ulrich

AU - Berger, Ralf G.

N1 - Funding information: This work was financed by the Deutsche Forschungsgemeinschaft (DFG KR 2958/1-1). We thank H. Ziegler for providing reference chemicals, F. Robic for her valuable assistance and D. Albert, Department of Organic Chemistry, Leibniz University of Hannover, for his support in NMR analysis.

PY - 2009/2/14

Y1 - 2009/2/14

N2 - 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.

AB - 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.

KW - β-Myrcene

KW - Endoperoxide

KW - Perillene

KW - Pleurotus sapidus

KW - Rose furane

UR - http://www.scopus.com/inward/record.url?scp=61549090583&partnerID=8YFLogxK

U2 - 10.1016/j.biortech.2009.01.001

DO - 10.1016/j.biortech.2009.01.001

M3 - Article

C2 - 19223179

AN - SCOPUS:61549090583

VL - 100

SP - 2855

EP - 2860

JO - Bioresource technology

JF - Bioresource technology

SN - 0960-8524

IS - 11

ER -