Photocatalysis as Powerful Tool For Polyene Cyclizations in Supramolecular Cages

Project Information

PhotoCage

Grant agreement ID: 101152106

DOI

10.3030/101152106

Project terminated on 30 June 2025

EC signature date 3 May 2024

Start date 1 June 2024

End date 31 May 2026

Funded under

• Marie Skłodowska-Curie Actions (MSCA)

Total cost

No data

EU contribution

€ 173 847,36

Coordinated by

UNIVERSITAT DES SAARLANDES
Germany

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

Reporting period: 2024-06-01 to 2026-05-31

Summary of the context and overall objectives of the project

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.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

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.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

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.