Enantioselective Addition of α‐Nitroesters to Alkynes

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 Rh III –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.