Ti(III)-Catalyzed Cyclizations of Ketoepoxypolyprenes: Control over the Number of Rings and Unexpected Stereoselectivities

We describe a new strategy to control the number of cyclization steps in bioinspired radical (poly)­cyclizations involving epoxypolyenes containing keto units positioned along the polyene chain. This approach provides an unprecedentedly straightforward access to natural terpenoids with pendant unsaturated side chains. Additionally, in the case of bi- and tricyclizations, decalins with <i>cis</i> stereochemistry have been obtained as a consequence of the presence of the ketone. The preferential formation of <i>cis</i>-fused adducts was rationalized using DFT calculations. This result is completely unprecedented in biomimetic cyclizations and permits the access to natural terpenoids with this stereochemistry, as well as to non-natural analogues

Ti(III)-Catalyzed Cyclizations of Ketoepoxypolyprenes: Control over the Number of Rings and Unexpected Stereoselectivities

We describe a new strategy to control the number of cyclization steps in bioinspired radical (poly)­cyclizations involving epoxypolyenes containing keto units positioned along the polyene chain. This approach provides an unprecedentedly straightforward access to natural terpenoids with pendant unsaturated side chains. Additionally, in the case of bi- and tricyclizations, decalins with <i>cis</i> stereochemistry have been obtained as a consequence of the presence of the ketone. The preferential formation of <i>cis</i>-fused adducts was rationalized using DFT calculations. This result is completely unprecedented in biomimetic cyclizations and permits the access to natural terpenoids with this stereochemistry, as well as to non-natural analogues

Development of a New Dual Polarity and Viscosity Probe Based on the Foldamer Concept

Small molecular probes able to act as sensors are of enormous interest thanks to their multiple applications. Here, we report on the development of a novel supramolecular dual viscosity and polarity probe based on the foldamer concept, which increases the resolution limits of traditional probes at low viscosity values (0–4 mPa·s). The applicability of this new probe has been tested with a supramolecular organogel