Chemoenzymatic Generation of Thio-analogues of δ-Cadinene, δ-Cadinol, and a Thio-diquinane Using 8-Thio-farnesylpyrophosphate

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OriginalspracheEnglisch
Seiten (von - bis)1653-1662
Seitenumfang10
FachzeitschriftJournal of natural products
Jahrgang88
Ausgabenummer7
Frühes Online-Datum17 Juli 2025
PublikationsstatusVeröffentlicht - 25 Juli 2025

Abstract

The synthesis of 8-thio-farnesylpyrophosphate is reported, which was subjected to biotransformations with different sesquiterpene synthases. The 9-thio-analogues of δ-cadinene and δ-cadinol were formed by the sesquiterpene synthases Cop4 and Omp7. In contrast, the fungal sesquiterpene synthase BcBOT2 yielded a diquinane terpenoid that contains a keto and thiol group. The formation of the two former "sulfo"-terpenoids can be rationalized by following the route proposed for δ-cadinene and δ-cadinol. The latter can be regarded by the result of a late-stage hydrolysis product during the analogous pathway to presilphiperfolan-8β-ol, the natural product of BcBOT2. The olfactoric analysis of the three "sulfo"-sesuiterpenoids revealed a stale odor for the cadinene derivatives, whereas the ketothiol diquinane exhibits a spicy aroma with a subtle chili note.

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Chemoenzymatic Generation of Thio-analogues of δ-Cadinene, δ-Cadinol, and a Thio-diquinane Using 8-Thio-farnesylpyrophosphate. / Jäger, Birk; Budde, Jan Luca; Birke, Norman et al.
in: Journal of natural products, Jahrgang 88, Nr. 7, 25.07.2025, S. 1653-1662.

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Jäger B, Budde JL, Birke N, Hauke M, Kirschning A. Chemoenzymatic Generation of Thio-analogues of δ-Cadinene, δ-Cadinol, and a Thio-diquinane Using 8-Thio-farnesylpyrophosphate. Journal of natural products. 2025 Jul 25;88(7):1653-1662. Epub 2025 Jul 17. doi: 10.1021/acs.jnatprod.5c00409
Jäger, Birk ; Budde, Jan Luca ; Birke, Norman et al. / Chemoenzymatic Generation of Thio-analogues of δ-Cadinene, δ-Cadinol, and a Thio-diquinane Using 8-Thio-farnesylpyrophosphate. in: Journal of natural products. 2025 ; Jahrgang 88, Nr. 7. S. 1653-1662.
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AU - Budde, Jan Luca

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AU - Kirschning, Andreas

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AB - The synthesis of 8-thio-farnesylpyrophosphate is reported, which was subjected to biotransformations with different sesquiterpene synthases. The 9-thio-analogues of δ-cadinene and δ-cadinol were formed by the sesquiterpene synthases Cop4 and Omp7. In contrast, the fungal sesquiterpene synthase BcBOT2 yielded a diquinane terpenoid that contains a keto and thiol group. The formation of the two former "sulfo"-terpenoids can be rationalized by following the route proposed for δ-cadinene and δ-cadinol. The latter can be regarded by the result of a late-stage hydrolysis product during the analogous pathway to presilphiperfolan-8β-ol, the natural product of BcBOT2. The olfactoric analysis of the three "sulfo"-sesuiterpenoids revealed a stale odor for the cadinene derivatives, whereas the ketothiol diquinane exhibits a spicy aroma with a subtle chili note.

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