C-4-selective
functionalization of azlactones provides access to
α,α-disubstituted unnatural α-amino acids, which
has been extensively investigated in the past decades. However, a
vast majority of such transformations are two-electron transfer reactions.
Herein, leveraging on the persistent radical effect, we develop photocatalytic
energy transfer-enabled regioconvergent alkylation of azlactones with
redox-active esters via radical–radical couplings. This strategy
is extended to the utilization of simple alkanes as the radical precursors,
whereby the aryl redox-active esters play a dual role of an oxidant
and a hydrogen-atom-transfer agent. Notably, the excited state Ir(III)
photocatalyst enables selective activation of the unwanted imine products
through triplet energy transfer, delivering C-4-functionalized azlactones
with high regioselectivity. Both experimental investigations and density
functional theory calculations on the reaction mechanism were performed,
supporting EnT-enabled regioconvergent photocatalytic radical–radical
coupling reaction pathways.