Chemoselective reductive coupling of α, β-unsaturated esters and nitroarenes for sustainable synthesis of β-amino acid esters by a hierarchically porous cobalt nanocatalyst

[Display omitted] •Reusable Co/N-doped carbon catalyst.•Cheap and abundant feedstocks.•Reductive coupling.•High step and atom efficiency.•Chemoselective generation of β-amino acid esters. Reductive coupling of two unsaturated substances for the construction of functional molecules remains a significant challenge due to the difficulty in controlling the chemoselective reduction. Here, by developing a cobalt and nitrogen co-doped hierarchically porous carbon material (Co/N-HPNC) deriving from the homomorphic Zr-based metal-organic framework (MOF), we describe, for the first time, its application as a bifunctional catalyst for direct access to β-amino acid esters via chemoselective reductive hydroamination of the α, β-unsaturated esters with cheap and air-stable nitroarenes. The catalyst structure-performance relationship reveals that the N-dopants benefit the adsorption of the nitroarenes and protons, and the active cobalt species run the transfer hydrogenation of the nitroarenes, such a synergetic effect results in chemoselective formation of the desired products. The developed catalytic transformation proceeds with good substrate and functionality tolerance, the use of easily accessible and reusable base metal catalyst, operational simplicity, high step and atom efficiency, and easy applicability for further fabrication of functional molecules, which offers a sustainable platform for direct synthesis of valuable products from bulk raw materials.