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Development and Applications of Photostable Lewis Basic Isochalcogenourea Catalysts

Project description

Pathway to isochalcogenourea catalysts and beyond

Recent advancements in photocatalysis have resulted from the development of tunable photocatalysts and affordable energy sources, such as sunlight. There is increasing interest in combining organocatalysis with photocatalysis for dual catalytic transformations. However, the lack of efficient methods for utilising cheap feedstock chemicals in carboxylic acid oxidation has limited their applications. Supported by the Marie Skłodowska-Curie Actions programme, the PhotoCat project will design a scalable pathway to manufacturing novel conformally constrained photostable isochalcogenourea catalysts. Using these catalysts, the project will develop a revolutionary dual photocatalytic isomerisation process for the synthesis of fine chemical products.

Objective

In recent years applications of photocatalysis have developed rapidly, with the use of an abundant, cheap energy source (the sun or ambient light) combined with the development of tunable photocatalysts, allowing the facile generation of radicals via single electron transfer or excited state intermediates via energy transfer. Organocatalysis uses small organic molecules to promote enantioselective reactions and has been widely applied over the last two decades for the synthesis of enantioenriched products, with the 2022 Nobel Prize for Chemistry awarded for demonstrating the power of this methodology by MacMillan and List. Combining these two methods in dual catalytic transformations has been demonstrated, however the ability to promote such transformations that utilise abundant and cheap feedstock chemicals at the carboxylic acid oxidation level is a significant challenge, typically requiring tertiary amine Lewis base catalysts. However, utilising enantiopure tertiary amines with photocatalytic transformations is currently limited, due to the facile oxidation and subsequent degradation of the tertiary organocatalyst by the excited state photocatalyst.

In this context. this proposal will:
1. Deliver a scalable route to conformally constrained photostable isochalcogneourea catalysts based upon conformationally locked bicyclic catalysts that do not allow traditional oxidative degradation.
2. Utilise these isochalcogneourea catalysts to develop a dual photocatalytic isomerization of (E)-enone acids to their contra-thermodynamic (Z)-isomers followed by isochalcogenourea promoted acylative DKR for the synthesis of fine chemical products. This will be applied to the synthesis of 5- and 7 membered ring compounds as well as the synthesis of planar chiral species.

Fields of science (EuroSciVoc)

Keywords

Programme(s)

Topic(s)

Funding Scheme

HORIZON-TMA-MSCA-PF-EF - HORIZON TMA MSCA Postdoctoral Fellowships - European Fellowships

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Call for proposal

(opens in new window) HORIZON-MSCA-2025-PF

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Coordinator

THE UNIVERSITY COURT OF THE UNIVERSITY OF ST ANDREWS
Net EU contribution
€ 276 187,92
Address
NORTH STREET 66 COLLEGE GATE
KY16 9AJ ST ANDREWS
United Kingdom
Region
Scotland Eastern Scotland Clackmannanshire and Fife
Activity type
Higher or Secondary Education Establishments
Links
Total cost
No data