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Carboxylic Esters as Bifunctional Reagents in Decarboxylative Cross-Coupling Reactions and Alkene Functionalizations

Objective

Transition-metal catalyzed cross-coupling reactions have transformed carbon-carbon bond formation in complex organic molecules, revolutionizing fields like pharmaceutical and agrochemical industries, polymers, and natural product synthesis. Despite their vast applications, these reactions heavily rely on toxic organic halides and organometallic reagents that require multiple preparation steps and often lack stability. Carboxylic esters (RCOOE) offer a promising alternative as they are readily available, potentially bio-sourced, and can serve as bifunctional partners in cross-coupling reactions. The ester’s R and E groups can act as nucleophiles and electrophiles upon carbon dioxide extrusion, forming carbon-carbon bonds (R–E) by recombination in an exergonic transformation. However, unlocking the full potential of esters faces a significant kinetic challenge due to the difficult activation of strong C–O bonds. This challenge has limited applications to reactive substrates like allyl esters (E = allyl).
The DECAF project seeks to overcome these barriers by developing groundbreaking multi-catalyst cross-coupling reactions using dialkyl carboxylic esters (RCOOE with R, E = alkyl) as versatile and bifunctional reagents under visible-light irradiation. In the first Strand, DECAF will focus on generating reactive intermediates from the cleavage of ester C–O bonds. Their potential as cross-coupling partners will be demonstrated through the example of Heck-type couplings with alkenes. The second Strand will introduce an electron-borrowing strategy to enable the decarboxylative recombination of esters. This unified mechanistic approach will extend the application of carboxylic esters as bifunctional reagents to catalytic alkene transfer dialkylations and, ultimately, decarboxylative sulfonylations.

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Topic(s)

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Funding Scheme

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HORIZON-ERC - HORIZON ERC Grants

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Call for proposal

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(opens in new window) ERC-2025-STG

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Host institution

CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE CNRS
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.

€ 1 499 435,00
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.

€ 1 499 435,00

Beneficiaries (1)

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