Cooperative N-heterocyclic carbene/transition metal redox catalysis – COORECA

Aldehydes are key synthons in organic synthesis. They are known to react with N-heterocyclic carbenes (NHC) to form electron-rich Breslow intermediates which are capable of triggering single-electron transfer reactions. Related NHC-catalysed radical transformations of aldehydes constitute an emerging competitive area of research, which, despite remarkable methodologic developments within the last years, has clearly reached a limit in terms of redox accessible substrates. COORECA project aims to overcome these limitations in order to access to the whole palette of reaction partners through the implementation of cooperative NHC/transition metal promoted approaches. The strategy considers the catalytic reduction of organometallic and coordination metal complexes, which will then activate the former redox-inaccessible substrates. Thus, this project aims at developing original radical catalytic transformations for challenging substrate activations. Its strategy goes beyond conventional methodological approaches. It will be supported (and, in many cases, inspired) by experimental and theoretical studies dedicated to understand the mechanisms through the isolation of key intermediates, their reactivity and electrochemical properties. In addition, it will also pave the way for more sustainable processes by diminishing the amount of waste (avoiding stoichiometric metal reductants), employing simple set-ups, avoiding precious metals, employing readily accessible and cheap ligands and non-toxic organocatalysts. Ultimately, it will enrich the modern synthetic toolbox with novel highly chemoselective methodologies.