Department of Chemistry, University of Basel, Mattenstrasse 24a, 4058 Basel, Switzerland.
Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel.
J Am Chem Soc. 2020 Mar 25;142(12):5894-5900. doi: 10.1021/jacs.0c01464. Epub 2020 Mar 16.
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.
萜类化合物是天然产物中结构变化最多的一类。自然界中，许多不同结构的萜类化合物都是由单一种类的 I 型萜烯环化酶从单一底物中生成的。然而，这种反应性在人造系统的溶液中很难重现。在此，我们报告了迄今为止最短的三环倍半萜 presilphiperfolan-1β-ol 的合成方法，该方法利用超分子间-resorcinarene 胶囊作为关键步骤的催化剂。这种合成方法还可以获得天然产物的非天然衍生物，而这些衍生物是无法通过生物合成机制获得的。此外，本研究为 presilphiperfolanol 天然产物的生物合成提供了有用的见解，包括与提议的 caryophyllene 和 presilphiperfolanols 生物合成连接相一致的第一个实验证据。
