Exploration of red-light-mediated dual photoredox-organometallic catalysis for sustainable cross-electrophile couplings

Cross-electrophile coupling (XEC) reactions enable the formation of C-C and C-Heteroatom bonds from two electrophiles. This approach takes benefits from the broader availability of electrophiles, compared to nucleophilic partners, while limiting site-selectivity issues. As XEC reactions operate under mild reductive conditions, they also offer a good functional group tolerance. For these reasons, XEC strategy has gained an important interest these last 15 years.[1] At the same time, visible-light mediated transformations have been recognized as a sustainable approach in synthetic chemistry. Indeed, the use of visible-light offers a more environmentally benign approach to reach reactive intermediates while avoiding the use of thermal activations and/or of hazardous reagents.

We are currently interested in XEC reactions promoted by dual photoredox-organometallic catalysis (Scheme 1). Such strategy takes advantage of organometallic chemistry, combining the use of a photocatalytically active species (photocatalyst, electron donor-acceptor complex) for the generation of reactive intermediates upon absorption of light.[2] As a direct consequence, the use of metal reductants commonly used for XECs, is suppressed.  The aim of this project is to further extend our methodology toward the formation of C(sp²)-C(sp³) bonds using milder and more easily scalable conditions, by modulating the type of light used, which constitutes a key improvement. Hence, visible-light mediated processes mainly operate under purple (390 nm), blue (405, 427, 456 nm) and green (535 nm) light, however such wavelengths represent potential health risks, like photooxidative damages to the retina. In addition, their uses in industrial applications are restricted, due to the heat generated by the light irradiation that needs to be controlled, finally limited penetration depth is a main drawback. Therefore, we envision to develop red-light mediated dual photoredox-organometallic catalytic XEC reactions. By using photons of lower energy, we ambition to develop milder reaction conditions for the formation of C(sp²)-C(sp³) bonds from easily available electrophiles, enabling to make them scalable toward industrial development. Moreover, red photons offer a better penetration, both in reaction media, increasing the absorption energy efficiency, and in biological tissues, opening the door to longer-term biological applications that would allow to extend the scope of applications of our methodology.[3]

Université Paris Cité incarne l’évolution d’un Paris moderne et se positionne comme acteur clé de l'enseignement supérieur, de la recherche et de l'innovation en France, en Europe et à l'échelle internationale. Issue des pôles historiques de Paris Descartes, Paris Diderot et de l’IPGP, l'université s'engage à développer et à partager des savoirs au service de la société. Avec ses trois grandes facultés – Santé, Sciences, et Société & Humanités – elle se distingue par sa pluridisciplinarité. Accueillant 58 000 étudiants et abritant 142 laboratoires, elle met la recherche et la formation au cœur de sa mission.

Profil du candidat : 

Diplômé(e) d'un Master en chimie ou équivalent

Forte motivation pour contribuer à l’avancement de la recherche académique

Connaissances théoriques et pratiques en chimie organique 

Expérience en techniques analytiques pour analyser  et critiquer les résultats de réaction

Capacités organisationnelles

Aptitude à présenter des résultats scientiques oralement et par écrit