Department of Chemistry, University of Basel, Mattenstrasse 24a, 4002, Basel, Switzerland.
Department of Biosystems Science and Engineering, ETH Zurich, Mattenstrasse 26, 4058, Basel, Switzerland.
Angew Chem Int Ed Engl. 2023 Mar 27;62(14):e202218625. doi: 10.1002/anie.202218625. Epub 2023 Feb 23.
Terpenes represent the largest and the most diverse class of natural compounds. This is remarkable as the whole variety is accessed from just a handful of highly conserved linear precursors. Modification of the cyclization precursors would enable a dramatic expansion of the accessible chemical space. However, natural enzymes do not enable us to tap into this potential, as they do not tolerate larger deviations from the prototypical substrate structure. Herein we report that supramolecular capsule catalysis enables facile access to diverse and novel terpenoid skeletons that formally can be traced back to C3-phenyl, benzyl, and homoprenyl derivatives of farnesol. Novel skeletons related to the presilphiperfolane core structure, as well as novel neoclovene derivatives were accessed efficiently in only four synthetic steps. Importantly, the products obtained carry functional groups that may be readily derivatized further.
萜类化合物是最大和最多样化的天然化合物类别。这是非常显著的，因为整个萜类化合物的多样性仅来源于少数几种高度保守的线性前体。环化前体的修饰将能够显著扩大可及的化学空间。然而，天然酶并不能使我们利用这种潜力，因为它们不能容忍与原型底物结构的较大偏差。在此，我们报告超分子胶囊催化能够轻松获得多样化和新颖的萜类骨架，这些骨架形式上可以追溯到法呢醇的 C3-苯基、苄基和同异戊二烯基衍生物。仅通过四个合成步骤就可以有效地获得与前硅菲烷核心结构相关的新型骨架以及新型新克洛文衍生物。重要的是，获得的产物带有可进一步轻易衍生化的官能团。
