Dominating redox mechanisms in iron-mediated C-C bond formations: reactivity, new paradigms and applications

2026-07-22

Due to the ubiquity of the C-C bond in diverse areas such as pharmaceuticals, agrochemicals or materials, development of atom-economical and efficient methods ensuring its formation is an active research field. This field witnessed incredible breakthroughs during the last decades, especially thanks to organometallic catalysis applied to cross-coupling or C-H activation methods. However, the most efficient C-C bond formation reactions rely on noble-metal catalysts, which lead to economic and toxicity issues. Iron catalysis appears as a promising alternative, since this metal is cheap and environmentally-friendly. Yet, current methods of Fe-mediated C-C bond formation suffer from strong scope limitations and lead to processes with a poor atom economy, as they often require stoichiometric organometallics or sacrificial reactants (metalation reagents, or oxidants). Dominating the reactivity of the C-Fe bond is pivotal to address those issues, since organoiron derivatives are key intermediates in Fe-mediated C-C bond formations. This reactivity is rich and complex, and is governed both by redox and spin effects. The DoReMI project aims to use this complexity as an advantage to develop new synthetic strategies, which cannot be envisioned with noble metal catalysis, aiming at overtaking the aforementioned pitfalls. In a first work package (WP1), the mechanistic features of the reaction of organoirons with electrophiles will be unveiled, shedding light on the reactivity of the C-Fe bond in a C-C bond formation context. WP2 will show for the first time that a stoichiometric C-H functionalization reaction between non-activated hydrocarbons and electrophiles can be achieved via the formation of an organoiron intermediate. Using the results gathered in WP1 and WP2, WP3 will demonstrate that this C-H functionalization methodology can be turned into an efficient catalytic method applicable to both unfunctionalized C-H substrates and to targets of synthetic interest.

France

2026-02-01