By using Rh–H catalysis, we couple α‐nitroesters and alkynes to prepare α‐amino‐acid precursors. This atom‐economical strategy generates two contiguous stereocenters, with high enantio‐ and diastereocontrol. In this transformation, the alkyne undergoes isomerization to generate a RhIII–π‐allyl electrophile, which is trapped by an α‐nitroester nucleophile. A subsequent reduction with In powder transforms the allylic α‐nitroesters to the corresponding α,α‐disubstituted α‐amino esters.

By using Rh–H catalysis, we couple α‐nitroesters and alkynes to prepare α‐amino‐acid precursors. This atom‐economical strategy generates two contiguous stereocenters, with high enantio‐ and diastereocontrol. In this transformation, the alkyne undergoes isomerization to generate a RhIII–π‐allyl electrophile, which is trapped by an α‐nitroester nucleophile. A subsequent reduction with In powder transforms the allylic α‐nitroesters to the corresponding α,α‐disubstituted α‐amino esters.

Designer amino acids find use across many scientific disciplines. The preparation of amino acids bearing acyclic vicinal stereocenters remains a challenge in synthesis. Herein, we highlight transition-metal catalyzed allylations for the stereoselective synthesis of disubstituted α-amino acid precursors bearing vicinal stereocenters. Allylation of azlactones, α-imino esters, and aldimine esters with dienes and allylic leaving groups are among the most common strategies. These developments provide context for our work featuring the asymmetric addition of α-nitroesters to alkynes.