Light‐Induced Chiral Aldehyde/Palladium Catalysis‐Enabled Asymmetric Allylic C─H Alkylation of Alkenes With NH 2 ‐Unprotected Amino Acid Derivatives

ABSTRACT The catalytic asymmetric allylic C–H alkylation of alkenes with the α‐carbon of readily available amino acid derivatives represents an ideal strategy for constructing chiral nonproteinogenic α,α‐disubstituted amino acids. However, such synthetic methodologies remain unexplored. Herein, we report a light‐induced, chiral aldehyde/palladium catalysis‐enabled direct allylic C–H alkylation of allyl arenes and 1,4‐enynes using NH 2 ‐unprotected amino acid esters. The results demonstrate that competing allylic C–H amination is completely suppressed, and the desired alkylation products—bearing either allyl or conjugated enyne moieties—are obtained in 32%–93% yields with 80%–98% ee values. Mechanistic studies reveal that enantiocontrol is achieved through the cooperative action of the chiral aldehyde and the chiral ligand, and the latter primarily dictates the absolute configuration of the product by forming noncovalent C–H···π and C–H···O interactions with the chiral aldehyde‐involved Zn complex.