Photocatalyzed Radical Cross-Coupling of Allylic Esters with <i>N</i> -Aryl Glycinates and Benzyl Amines for sp ³ C–C Bond Formation

The allylic moiety is a prevalent structural motif in pharmaceuticals and bioactive molecules, offering significant synthetic versatility. The conventional Tsuji–Trost reaction relies on transition metal catalysis and preactivated carbon nucleophiles (such as malonates), which often constrain functional group compatibility and reaction diversity. This study introduces a direct radical–radical cross-coupling strategy that capitalizes on polarity matching between π-allylic radicals and amine α-alkyl radicals to facilitate C(sp 3 )–C(sp 3 ) bond formation. The approach demonstrates remarkable substrate versatility and functional group compatibility, enabling late-stage derivatization of diverse natural products. The reaction also achieves enantioselective control through chiral auxiliaries, such as (−)-menthol, underscoring its synthetic potential.