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, but 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 direct experimental evidence for the proposed biosynthetic connection between caryophyllene and the presilphiperfolanols.

At opologically well-defined atropisomeric teraryl monophosphine ligand system, prepared by ah ighly stereoselective arene-forming aldol condensation combined with ad irect ester-to-anthracene transformation, is described herein. The ligands were evaluated for gold(I)catalyzed [2+ +2] cycloadditiona nd cycloisomerization reactions as well as au nique intramolecular Pd-catalyzedC ÀN cross-coupling for the atroposelective synthesis of a Naryl-indolineb earing aC ÀNs tereogenic axis. The ligand structure induced up to 95:5 stereoselectivity in the asymmetric allylic alkylation reaction and features an interesting dynamic behavior as observed by X-ray crystallographic studies.

The scope of the trimerization reaction of 3-substituted benzyl alcohols was explored. Several C 3-symmetric cyclotribenzylene derivatives were obtained in preparative useful yields in one step and applied to the short synthesis (one or two steps) of two CTB derivatives, so far only accessible in six or seven linear steps.