Photoinduced Palladium Catalysis Enables Dynamic Kinetic Asymmetric Allylic Imidation.

Palladium (Pd)-catalyzed dynamic kinetic asymmetric transformation (DYKAT) provides a powerful approach to enantiomerically enriched molecules. Although well-established for monosubstituted and symmetric 1,3-disubstituted allylic substrates, the DYKAT of unsymmetrical 1,3-disubstituted systems remains a substantial challenge, with few general solutions reported. Here, we present a photoinduced Pd-catalyzed DYKAT that enables highly regio- and enantioselective imidation of unsymmetrical 1,3-disubstituted allylic electrophiles, including allyl esters, vinyl epoxides, and vinyl carbonates. This method delivers chiral allylamines and amino alcohols with up to >20:1 regioselectivity ratio and up to 99% enantiomeric excess. Mechanistic investigations reveal that visible-light excitation promotes rapid interconversion of two diastereomeric π-allyl Pd(II) intermediates. This process involves a key equilibrium between a Pd species and an allyl radical, which is essential for achieving enantioconvergent conversion under mild conditions.