Expanding the “Terpenome”: Applications of Unspecific Peroxygenases (UPOs) in Oxidations of Unnatural Terpenoids

Henry Struwe; Christopher Grimm; Gerald Dräger; Sascha Beutel; Miguel Alcalde; Andreas Kirschning; Selin Kara

doi:10.1002/cctc.202401414

Expanding the “Terpenome”: Applications of Unspecific Peroxygenases (UPOs) in Oxidations of Unnatural Terpenoids

Henry Struwe
, Christopher Grimm
, Gerald Dräger
, Sascha Beutel
, Miguel Alcalde
, Andreas Kirschning^*
, Selin Kara^*

^*Corresponding author af dette arbejde

Institut for Bio- og Kemiteknologi - Bioprocess Engineering, Gustav Wieds Vej 10D

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

1 Citationer (Scopus)

15 Downloads (Pure)

Abstract

An unnatural tricyclic oxaterpenoid, obtained by treatment of the sesquiterpene synthase presilphiperfolan-8β-ol synthase (BcBOT2) with an unnatural farnesyl pyrophosphate ether derivative, itself obtained by chemical synthesis, was converted in oxidation studies as part of a broad screening program by selected unspecific peroxygenases (UPOs). Product analysis revealed that Agrocybe aegerita UPO, its mutant PaDa-I, and two commercial ones, UPO₅₄ and UPO_49, provided new oxidation products with sufficient efficiency for subsequent upscaling that allowed product isolation and structure elucidation. As such new terpene-based oxiranes and hemiacetals were formed by UPO-mediated epoxidations and CH-activation. The structure elucidation was further supported by comparison with products generated by chemical oxidation.

Originalsprog	Engelsk
Artikelnummer	e202401414
Tidsskrift	ChemCatChem
Vol/bind	17
Nummer	1
ISSN	1867-3880
DOI	https://doi.org/10.1002/cctc.202401414
Status	Udgivet - jan. 2025

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10.1002/cctc.202401414

ChemCatChem - 2024 - Struwe - Expanding the Terpenome Applications of Unspecific Peroxygenases UPOs in Oxidations ofForlagets udgivne version, 1,01 MBLicens: CC BY-NC

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title = "Expanding the “Terpenome”: Applications of Unspecific Peroxygenases (UPOs) in Oxidations of Unnatural Terpenoids",

abstract = "An unnatural tricyclic oxaterpenoid, obtained by treatment of the sesquiterpene synthase presilphiperfolan-8β-ol synthase (BcBOT2) with an unnatural farnesyl pyrophosphate ether derivative, itself obtained by chemical synthesis, was converted in oxidation studies as part of a broad screening program by selected unspecific peroxygenases (UPOs). Product analysis revealed that Agrocybe aegerita UPO, its mutant PaDa-I, and two commercial ones, UPO54 and UPO49, provided new oxidation products with sufficient efficiency for subsequent upscaling that allowed product isolation and structure elucidation. As such new terpene-based oxiranes and hemiacetals were formed by UPO-mediated epoxidations and CH-activation. The structure elucidation was further supported by comparison with products generated by chemical oxidation.",

keywords = "Biocatalysis, CH-activation, Terpene synthases, Terpenoids, Unspecific peroxygenases",

author = "Henry Struwe and Christopher Grimm and Gerald Dr{\"a}ger and Sascha Beutel and Miguel Alcalde and Andreas Kirschning and Selin Kara",

note = "Publisher Copyright: {\textcopyright} 2024 The Author(s). ChemCatChem published by Wiley-VCH GmbH.",

year = "2025",

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doi = "10.1002/cctc.202401414",

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T2 - Applications of Unspecific Peroxygenases (UPOs) in Oxidations of Unnatural Terpenoids

AU - Struwe, Henry

AU - Grimm, Christopher

AU - Dräger, Gerald

AU - Beutel, Sascha

AU - Alcalde, Miguel

AU - Kirschning, Andreas

AU - Kara, Selin

PY - 2025/1

Y1 - 2025/1

N2 - An unnatural tricyclic oxaterpenoid, obtained by treatment of the sesquiterpene synthase presilphiperfolan-8β-ol synthase (BcBOT2) with an unnatural farnesyl pyrophosphate ether derivative, itself obtained by chemical synthesis, was converted in oxidation studies as part of a broad screening program by selected unspecific peroxygenases (UPOs). Product analysis revealed that Agrocybe aegerita UPO, its mutant PaDa-I, and two commercial ones, UPO54 and UPO49, provided new oxidation products with sufficient efficiency for subsequent upscaling that allowed product isolation and structure elucidation. As such new terpene-based oxiranes and hemiacetals were formed by UPO-mediated epoxidations and CH-activation. The structure elucidation was further supported by comparison with products generated by chemical oxidation.

AB - An unnatural tricyclic oxaterpenoid, obtained by treatment of the sesquiterpene synthase presilphiperfolan-8β-ol synthase (BcBOT2) with an unnatural farnesyl pyrophosphate ether derivative, itself obtained by chemical synthesis, was converted in oxidation studies as part of a broad screening program by selected unspecific peroxygenases (UPOs). Product analysis revealed that Agrocybe aegerita UPO, its mutant PaDa-I, and two commercial ones, UPO54 and UPO49, provided new oxidation products with sufficient efficiency for subsequent upscaling that allowed product isolation and structure elucidation. As such new terpene-based oxiranes and hemiacetals were formed by UPO-mediated epoxidations and CH-activation. The structure elucidation was further supported by comparison with products generated by chemical oxidation.

KW - Biocatalysis

KW - CH-activation

KW - Terpene synthases

KW - Terpenoids

KW - Unspecific peroxygenases

UR - https://www.scopus.com/pages/publications/85205899888

U2 - 10.1002/cctc.202401414

DO - 10.1002/cctc.202401414

M3 - Journal article

AN - SCOPUS:85205899888

SN - 1867-3880

VL - 17

JO - ChemCatChem

JF - ChemCatChem

IS - 1

M1 - e202401414

ER -

Expanding the “Terpenome”: Applications of Unspecific Peroxygenases (UPOs) in Oxidations of Unnatural Terpenoids

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