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

Project description

C(sp3)-C bond formation via low-valent bismuth catalysis and electrochemistry

Carbon-carbon (C-C) bonds are the backbone of organic molecules and are therefore essential to organic chemistry and the synthesis of innumerable organic molecules, both known and predicted/desired. However, forming these bonds can be challenging; C(sp3) carboxylation and C(sp3)-C(sp3) coupling reactions are among the transformations that remain difficult to achieve, even with transition metal catalysis. With the support of the Marie Skłodowska-Curie Actions programme, the Bi-echem project aims to enable sustainable C-C bond formation by merging low-valent bismuth catalysis with electrochemistry. This will be the first systematic investigation of electrocatalytic organobismuth frameworks for the synthesis of organic molecules, with a focus on C(sp3) carboxylation and C(sp3)-C(sp3) coupling reactions.

Objective

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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Coordinator

MAX PLANCK INSTITUT FUER KOHLENFORSCHUNG
Net EU contribution
€ 189 687,36
Address
KAISER WILHELM PLATZ 1
45470 Muelheim An Der Ruhr
Germany

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Region
Nordrhein-Westfalen Düsseldorf Mülheim an der Ruhr
Activity type
Research Organisations
Links
Total cost
No data