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
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.
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 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.
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.
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.