Stereodivergent Four-Component Reactions via Rh-Carbynoids

Multicomponent reactions (MCRs) provide a robust platform for the modular assembly of structurally complex molecules, while higher-order MCRs (≥4 components) exponentially expand the accessible chemical space. Although Rh-carbynoids exhibit significant potential for developing higher-order MCRs due to their unique reactivity, their application in asymmetric four-component reactions (4CRs) has been hindered by competing nucleophilic reactivities and stereochemical control. Herein, we overcome these challenges by integrating <i>N</i>- and <i>C</i>-nucleophiles and report an asymmetric 4CR involving hypervalent iodine diazo reagents, carbamates, <i>N,N</i>-dialkylanilines, and imines. This strategy represents the first asymmetric 4CR utilizing Rh-carbynoids, achieving the sequential formation of C(sp³)-N, C(sp³)-C(sp²), and C(sp³)-C(sp³) bonds at a single carbon center. The method provides stereodivergent access to α,β-diamino-3-arylpropanoic acid derivatives bearing two contiguous stereocenters with good yields and exceptional enantioselectivity.