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Photoinduced Enantioselective C-H Bond Arylation of Carbonyls via Aryl Thianthrenium Salts

Project description

Enantioselective arylation of carbonyls using abundant materials under mild conditions

Arylation of carbonyl compounds (adding carbon rings to compounds like ketones, aldehydes or esters) in an enantioselective way is a powerful but challenging step in pharmaceutical and agrochemical discovery. Current methods rely on costly, prefunctionalised reagents and chiral rare metal catalysts. With the support of the Marie Skłodowska-Curie Actions programme, the PEARL project aims to develop a simpler, more sustainable alternative. Its multi-catalytic platform will use visible-light-driven catalysis to decarboxylate abundant aryl carboxylic acids to produce aryl thianthrenium salts. Chiral amine catalysis will achieve precise, enantioselective arylation using the salts under mild conditions and releasing only CO₂ as a by-product. This approach could significantly streamline sustainable drug and agrochemical discovery.

Objective

The enantioselective arylation of carbonyl compounds is a powerful yet demanding transformation with broad applications in pharmaceutical and agrochemical discovery. Current methods typically require prefunctionalised aryl reagents and costly chiral metal complexes, limiting both scope and sustainability. This project proposes a multicatalytic platform that combines visible-light-driven Cu-catalysed decarboxylation of aryl carboxylic acids to generate aryl thianthrenium salts in situ with chiral amine catalysis via electron donor–acceptor (EDA) complex activation. This strategy employs abundant carboxylic acids as renewable aryl sources, releases only CO2 as a by-product, and delivers high enantioselectivity under mild conditions. Mechanistic investigations will probe radical intermediates and the role of EDA complexes in asymmetric bond formation, providing fundamental insights into multicatalytic photochemical systems. The methodology will enable direct α- and γ-functionalisation of carbonyl compounds, streamline access to enantioenriched scaffolds, and expand the synthetic utility of carboxylic acids as sustainable building blocks.

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Topic(s)

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

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Call for proposal

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

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Coordinator

THE CHANCELLOR MASTERS AND SCHOLARS OF THE UNIVERSITY OF CAMBRIDGE
Net EU contribution

Net EU financial contribution. The sum of money that the participant receives, deducted by the EU contribution to its linked third party. It considers the distribution of the EU financial contribution between direct beneficiaries of the project and other types of participants, like third-party participants.

€ 276 187,92
Address
TRINITY LANE THE OLD SCHOOLS
CB2 1TN CAMBRIDGE
United Kingdom

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Region
East of England East Anglia Cambridgeshire CC
Activity type
Higher or Secondary Education Establishments
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Total cost

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