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.
Tandem catalysis enables the rapid
construction of complex architectures
from simple building blocks. This Perspective shares our interest
in combining stereoselective hydrogenation with transformations
such as isomerization, oxidation, and epimerization to solve diverse
challenges. We highlight the use of tandem hydrogenation for preparing
complex natural products from simple prochiral building blocks and
present tandem catalysis involving transfer hydrogenation and dynamic
kinetic resolution. Finally, we underline recent breakthroughs and
opportunities for asymmetric hydrogenation.
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.
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