Details
| Original language | English |
|---|---|
| Pages (from-to) | 17838-17846 |
| Number of pages | 9 |
| Journal | Journal of the American Chemical Society |
| Volume | 146 |
| Issue number | 26 |
| Early online date | 18 Jun 2024 |
| Publication status | Published - 3 Jul 2024 |
Abstract
Presilphiperfolan-8β-ol synthase (BcBOT2), a substrate-promiscuous sesquiterpene cyclase (STC) of fungal origin, is capable of converting two new farnesyl pyrophosphate (FPP) derivatives modified at C7 of farnesyl pyrophosphate (FPP) bearing either a hydroxymethyl group or a methoxymethyl group. These substrates were chosen based on a computationally generated model. Biotransformations yielded five new oxygenated terpenoids. Remarkably, the formation of one of these tricyclic products can only be explained by a cationically induced migration of the methoxy group, presumably via a Meerwein-salt intermediate, unprecedented in synthetic chemistry and biosynthesis. The results show the great principle and general potential of terpene cyclases for mechanistic studies of unusual cation chemistry and for the creation of new terpene skeletons.
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- General Chemistry
- Biochemistry, Genetics and Molecular Biology(all)
- Biochemistry
- Chemical Engineering(all)
- Colloid and Surface Chemistry
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In: Journal of the American Chemical Society, Vol. 146, No. 26, 03.07.2024, p. 17838-17846.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Sesquiterpene Cyclase BcBOT2 Promotes the Unprecedented Wagner-Meerwein Rearrangement of the Methoxy Group
AU - Moeller, Malte
AU - Dhar, Dipendu
AU - Dräger, Gerald
AU - Özbasi, Mikail
AU - Struwe, Henry
AU - Wildhagen, Maik
AU - Davari, Mehdi D.
AU - Beutel, Sascha
AU - Kirschning, Andreas
N1 - Publisher Copyright: © 2024 The Authors. Published by American Chemical Society.
PY - 2024/7/3
Y1 - 2024/7/3
N2 - Presilphiperfolan-8β-ol synthase (BcBOT2), a substrate-promiscuous sesquiterpene cyclase (STC) of fungal origin, is capable of converting two new farnesyl pyrophosphate (FPP) derivatives modified at C7 of farnesyl pyrophosphate (FPP) bearing either a hydroxymethyl group or a methoxymethyl group. These substrates were chosen based on a computationally generated model. Biotransformations yielded five new oxygenated terpenoids. Remarkably, the formation of one of these tricyclic products can only be explained by a cationically induced migration of the methoxy group, presumably via a Meerwein-salt intermediate, unprecedented in synthetic chemistry and biosynthesis. The results show the great principle and general potential of terpene cyclases for mechanistic studies of unusual cation chemistry and for the creation of new terpene skeletons.
AB - Presilphiperfolan-8β-ol synthase (BcBOT2), a substrate-promiscuous sesquiterpene cyclase (STC) of fungal origin, is capable of converting two new farnesyl pyrophosphate (FPP) derivatives modified at C7 of farnesyl pyrophosphate (FPP) bearing either a hydroxymethyl group or a methoxymethyl group. These substrates were chosen based on a computationally generated model. Biotransformations yielded five new oxygenated terpenoids. Remarkably, the formation of one of these tricyclic products can only be explained by a cationically induced migration of the methoxy group, presumably via a Meerwein-salt intermediate, unprecedented in synthetic chemistry and biosynthesis. The results show the great principle and general potential of terpene cyclases for mechanistic studies of unusual cation chemistry and for the creation of new terpene skeletons.
UR - http://www.scopus.com/inward/record.url?scp=85196714803&partnerID=8YFLogxK
U2 - 10.1021/jacs.4c03386
DO - 10.1021/jacs.4c03386
M3 - Article
C2 - 38888422
AN - SCOPUS:85196714803
VL - 146
SP - 17838
EP - 17846
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 26
ER -