Bi-echem | Merging low-valent Bi redox catalysis with electrochemistry for the formation of C(sp3)-C bonds

Summary
The proposed work involves merging low-valent bismuth catalysis with electrochemistry to unlock eminently sustainable methods for C-C bond formation. The research outlined herein would constitute the first systematic foray into electrocatalytic organobismuth manifolds for the synthesis of organic molecules.

Well-defined monomeric Bi(I) pincer complexes have recently been used to activate redox-active esters and alkyl halides via 1-electron and 2-electron pathways, respectively. In the first section, we propose a systematic electrochemical characterization of several N,C,N-Bi(III) pincer complexes, with particular emphasis on identifying the reversibility and potential of distinct redox states accessible by each complex. The cathodic reduction of Bi(III) species to their Bi(I) counterparts will also be performed in the presence of alkyl electrophiles to afford Bi(III)-alkyl species. The insights obtained from these foundational studies will be applied in the context of developing electrocatalytic manifolds for the C(sp3) carboxylation and C(sp3)-C(sp3) coupling reactions, two transformations that remain challenging even in the context of transition metal catalysis.
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More information & hyperlinks
Web resources: https://cordis.europa.eu/project/id/101151827
Start date: 01-05-2024
End date: 30-04-2026
Total budget - Public funding: - 189 687,00 Euro
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Original description

The proposed work involves merging low-valent bismuth catalysis with electrochemistry to unlock eminently sustainable methods for C-C bond formation. The research outlined herein would constitute the first systematic foray into electrocatalytic organobismuth manifolds for the synthesis of organic molecules.

Well-defined monomeric Bi(I) pincer complexes have recently been used to activate redox-active esters and alkyl halides via 1-electron and 2-electron pathways, respectively. In the first section, we propose a systematic electrochemical characterization of several N,C,N-Bi(III) pincer complexes, with particular emphasis on identifying the reversibility and potential of distinct redox states accessible by each complex. The cathodic reduction of Bi(III) species to their Bi(I) counterparts will also be performed in the presence of alkyl electrophiles to afford Bi(III)-alkyl species. The insights obtained from these foundational studies will be applied in the context of developing electrocatalytic manifolds for the C(sp3) carboxylation and C(sp3)-C(sp3) coupling reactions, two transformations that remain challenging even in the context of transition metal catalysis.

Status

SIGNED

Call topic

HORIZON-MSCA-2023-PF-01-01

Update Date

06-10-2024
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Horizon Europe
HORIZON.1 Excellent Science
HORIZON.1.2 Marie Skłodowska-Curie Actions (MSCA)
HORIZON.1.2.0 Cross-cutting call topics
HORIZON-MSCA-2023-PF-01
HORIZON-MSCA-2023-PF-01-01 MSCA Postdoctoral Fellowships 2023