Photocatalysis as Powerful Tool For Polyene Cyclizations in Supramolecular Cages

Información del proyecto

PhotoCage

Identificador del acuerdo de subvención: 101152106

DOI

10.3030/101152106

Proyecto finalizado el 30 Junio 2025

Fecha de la firma de la CE 3 Mayo 2024

Fecha de inicio 1 Junio 2024

Fecha de finalización 31 Mayo 2026

Financiado con arreglo a

• Marie Skłodowska-Curie Actions (MSCA)

Coste total

Sin datos

Aportación de la UE

€ 173 847,36

Coordinado por

UNIVERSITAT DES SAARLANDES
Germany

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

Período documentado: 2024-06-01 hasta 2026-05-31

Resumen del contexto y de los objetivos generales del proyecto

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.

Trabajo realizado desde el comienzo del proyecto hasta el final del período abarcado por el informe y los principales resultados hasta la fecha

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.

Avances que van más allá del estado de la técnica e impacto potencial esperado (incluida la repercusión socioeconómica y las implicaciones sociales más amplias del proyecto hasta la fecha)

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.