Four-Step Access to the Sesquiterpene Natural Product Presilphiperfolan-1β-ol and Unnatural Derivatives via Supramolecular Catalysis

Leonidas Dimitrios Syntrivanis; Ivana Némethová; Dario Schmid; Shani Levi; Alessandro Prescimone; Fabian Bissegger; Dan T. Major; Konrad Tiefenbacher

doi:10.1021/jacs.0c01464

Four-Step Access to the Sesquiterpene Natural Product Presilphiperfolan-1β-ol and Unnatural Derivatives via Supramolecular Catalysis

Leonidas Dimitrios Syntrivanis, Ivana Némethová, Dario Schmid, Shani Levi, Alessandro Prescimone, Fabian Bissegger, Dan T. Major, Konrad Tiefenbacher

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

54 Scopus citations

Abstract

Terpenes constitute one of the most structurally varied classes of natural products. A wide range of these structures are produced in nature by type I terpene cyclase enzymes from one single substrate. However, such reactivity has proven difficult to reproduce in solution with man-made systems. Herein we report the shortest synthesis of the tricyclic sesquiterpene presilphiperfolan-1β-ol to date, utilizing the supramolecular resorcinarene capsule as catalyst for the key step. This synthetic approach also allows access to unnatural derivatives of the natural product, which would not be accessible through the biosynthetic machinery. Additionally, this study provides useful insight into the biosynthesis of the presilphiperfolanol natural products, including the first experimental evidence consistent with the proposed biosynthetic connection between caryophyllene and the presilphiperfolanols.

Original language	English
Pages (from-to)	5894-5900
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	142
Issue number	12
DOIs	https://doi.org/10.1021/jacs.0c01464
State	Published - 25 Mar 2020

Bibliographical note

Publisher Copyright:
Copyright © 2020 American Chemical Society.

Funding

This work was supported by funding from the European Research Council Horizon 2020 Programme [ERC Starting Grant 714620-TERPENECAT] and the Swiss National Science Foundation as part of the NCCR Molecular Systems Engineering.

Funders	Funder number
European Research Council Horizon 2020 Programme
NCCR Molecular Systems Engineering
Horizon 2020 Framework Programme	714620
European Commission
Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung

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10.1021/jacs.0c01464

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title = "Four-Step Access to the Sesquiterpene Natural Product Presilphiperfolan-1β-ol and Unnatural Derivatives via Supramolecular Catalysis",

abstract = "Terpenes constitute one of the most structurally varied classes of natural products. A wide range of these structures are produced in nature by type I terpene cyclase enzymes from one single substrate. However, such reactivity has proven difficult to reproduce in solution with man-made systems. Herein we report the shortest synthesis of the tricyclic sesquiterpene presilphiperfolan-1β-ol to date, utilizing the supramolecular resorcinarene capsule as catalyst for the key step. This synthetic approach also allows access to unnatural derivatives of the natural product, which would not be accessible through the biosynthetic machinery. Additionally, this study provides useful insight into the biosynthesis of the presilphiperfolanol natural products, including the first experimental evidence consistent with the proposed biosynthetic connection between caryophyllene and the presilphiperfolanols.",

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AU - Némethová, Ivana

AU - Schmid, Dario

AU - Levi, Shani

AU - Prescimone, Alessandro

AU - Bissegger, Fabian

AU - Major, Dan T.

AU - Tiefenbacher, Konrad

PY - 2020/3/25

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AB - Terpenes constitute one of the most structurally varied classes of natural products. A wide range of these structures are produced in nature by type I terpene cyclase enzymes from one single substrate. However, such reactivity has proven difficult to reproduce in solution with man-made systems. Herein we report the shortest synthesis of the tricyclic sesquiterpene presilphiperfolan-1β-ol to date, utilizing the supramolecular resorcinarene capsule as catalyst for the key step. This synthetic approach also allows access to unnatural derivatives of the natural product, which would not be accessible through the biosynthetic machinery. Additionally, this study provides useful insight into the biosynthesis of the presilphiperfolanol natural products, including the first experimental evidence consistent with the proposed biosynthetic connection between caryophyllene and the presilphiperfolanols.

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Four-Step Access to the Sesquiterpene Natural Product Presilphiperfolan-1β-ol and Unnatural Derivatives via Supramolecular Catalysis

Abstract

Bibliographical note

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