Photocatalysis as Powerful Tool For Polyene Cyclizations in Supramolecular Cages

Projektinformationen

PhotoCage

ID Finanzhilfevereinbarung: 101152106

DOI

10.3030/101152106

Das Projekt endete am 30 Juni 2025

EK-Unterschriftsdatum 3 Mai 2024

Startdatum 1 Juni 2024

Enddatum 31 Mai 2026

Finanziert unter

• Marie Skłodowska-Curie Actions (MSCA)

Gesamtkosten

Keine Daten

EU-Beitrag

€ 173 847,36

Koordiniert durch

UNIVERSITAT DES SAARLANDES
Germany

Periodic Reporting for period 1 - PhotoCage (Photocatalysis as Powerful Tool For Polyene Cyclizations in Supramolecular Cages)

Berichtszeitraum: 2024-06-01 bis 2026-05-31

Zusammenfassung vom Kontext und den Gesamtzielen des Projekts

PhotoCage is based on the study of the interaction between photocatalysts and fluorinated alcohols. In this context, fluorinated alcohols are very special solvents in organic chemistry due to their extraordinary chemical and physical properties (e. g. strong H-bonding donor ability, low nucleophilicity). The combination of fluorinated alcohols with PET processes makes this strategy unique for developing new transformations. To achieve PhotoCage, 3 main research objectives were studied: (a) Design of the supramolecular cage photocatalyst and study of the interaction between them; (b) Application of the designed supramolecular cage photocatalyst to new organic reactions; (c) Study of the reaction mechanisms.
During the development of the project, we discovered that Eosin Y can disproportionate in two species (EH· and EH3·) in the presence of fluorinated solvents promoting alkene oxidation beyond their oxidation potential. As a result, different intra- and inter- alkene's functionalizations could be achieved.
Thus, this finding will allow us to explore multiple alkene functionalizations using different classes of nucleophiles.

Arbeit, die ab Beginn des Projekts bis zum Ende des durch den Bericht erfassten Berichtszeitraums geleistet wurde, und die wichtigsten bis dahin erzielten Ergebnisse

Work Package 1 - [WP1: Design of the supramolecular cage photocatalyst and study of the interaction between them. (Months 1-6). Discovery of the Photocatalytic Eosin Y Disproportionation as Driving Force for Terpene Cyclizations.


Work Package 2 - [Application of the designed supramolecular cage – photocatalyst to polyene cyclizations (Month 1-12)]. Development of unreactive alkene's hydrofunctionalizations.


Work Package 3 - [WP3: Mechanistic pathway establishment (months 7-12). Detection of reaction intermediates via radical trapping experiments.

Fortschritte, die über den aktuellen Stand der Technik hinausgehen und voraussichtliche potenzielle Auswirkungen (einschließlich der bis dato erzielten sozioökonomischen Auswirkungen und weiter gefassten gesellschaftlichen Auswirkungen des Projekts)

We discovered that Eosin Y can disproportionate in two species (EH· and EH3·) in the presence of fluorinated solvents promoting alkene oxidation beyond their oxidation potential. As a result, different intra- and inter- alkene's functionalizations could be achieved. Importantly, this achievement opens a new research topic within alkene functionalizations via radical chemistry due to the exclusive Markovnikov selectivity observed in comparison with traditional radical chemistry, where anti-Markovnikov is prefered.