June 13，2025

Congrats to Yan Luo et al. for the latest publication in Nat. Chem. We have developed a dirhodium/Xantphos or dirhodium-palladium dual catalyzed three-component reaction of diazo compounds, allylic electrophiles, and DMF was disclosed, to afford a wide variety of highly functionalized tertiary amine products. Notably, a large diversity of diazo esters, formamides and allylic substrates can be applied in this reaction, providing a variety of interesting molecules with an extensively rearranged skeleton, including α-aminoketones, ring-extended structures and cyclopentenones, in a highly atom-economical and step-efficient way. Combined experimental mechanistic investigation and DFT calculations suggested that a dyotropic type rearrangement of the in situ formed amino epoxy intermediate is the key for the current catalytic Domino process.