Photocatalyzed Radical Cross-Coupling of Allylic Esters with N-Aryl Glycinates and Benzyl Amines for sp3 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(sp3)-C(sp3) 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.