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ortho-Disubstituted Arenes as Orthogonal Organophotocatalysts for Reduction and Cross-Coupling Reactions

Objective

Organocatalytic analogues of transition metal catalysts can future-proof organic synthesis against the depletion of metals, improve the sustainability of chemical production, circumvent catalyst deactivation by Lewis-basic motifs, and avoid toxic metal impurities in drugs. Organocatalytic strategies for the reduction of unactivated C=C bonds and the C–C cross-coupling of unactivated halides, which are among the most common transformations in medicinal chemistry, remain difficult to develop with broad scope as oxidative substrate activation requires highly reactive species. Photocatalysis is a potential solution since it can selectively activate even unreactive motifs under mild conditions. Yet, the generated open-shell species are often difficult to control without a metal co-catalyst. EDA complexes, which have emerged as a photocatalyst-free means for light-mediated reactions, in principle, enable selective transformations without a metal co-catalyst by proximity-control within contact ion pairs. In practice, however, such reactions often depend on a fragmentation step that generates free radicals, which are subject to the same limitations as those generated by classical photocatalysis. Project ORTHOCAT aims to achieve selective organophotocatalytic C=C bond reduction and C–C cross-coupling reactions via rearrangement reactions of contact ion pairs derived from EDA complexes with ortho-disubstituted arenes. The key design principle is the bond polarization upon single electron transfer, which enables a nucleophilic substitution step that mimics migratory insertion or reductive elimination steps of transition metal mediated reactions. The successful development of this proposal will establish an orthogonal catalysis strategy, address the pervasive and vexing deactivation of Lewis-acidic metal catalysts in medicinal chemistry, and enable new transformations to sought-after motifs.

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Topic(s)

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HORIZON-ERC - HORIZON ERC Grants

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(opens in new window) ERC-2025-STG

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Host institution

BERGISCHE UNIVERSITAET WUPPERTAL
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.

€ 1 500 000,00
Address
GAUSS-STRASSE 20
42119 Wuppertal
Germany

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Region
Nordrhein-Westfalen Düsseldorf Wuppertal, Kreisfreie Stadt
Activity type
Higher or Secondary Education Establishments
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Total cost

The total costs incurred by this organisation to participate in the project, including direct and indirect costs. This amount is a subset of the overall project budget.

€ 1 500 000,00

Beneficiaries (1)

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