Imidazolium carboxylates boost Ru-catalyzed hydroaminomethylation of olefins with CO2

The valorization of CO2 presents a crucial challenge in the pursuit of carbon-neutral processes. Herein, we report the successful hydroaminomethylation of diverse alkenes with CO2 and H2, using N-heterocyclic carbene-Ru coordination assemblies as solid single-site catalysts. Intriguingly, the incorporation of imidazolium carboxylates was discovered to profoundly enhance CO2 activation, leading to excellent yields (up to 98%) and selectivity (up to 98%) toward upgraded amines across a broad substrate scope. Remarkably, a record-breaking turnover number of up to 1.8 × 104 was achieved. The robustness of the solid catalysts facilitated effortless recovery and enabled their reuse for over 10 cycles without any discernible loss in activity and selectivity, making this protocol practical and straightforward for CO2 valorization.