Donor–Acceptor–Donor Complex Enabled, Metal‐, and Photocatalyst‐Free Synthesis of NEK2 and Cumene Oxidation Inhibitors via Direct Decarboxylative Amination of N‐Aryl Glycines

The donor–acceptor–donor (DAD) complex model provides a reliable strategy for mediating direct decarboxylative coupling between two electron donors, effectively eliminating the need for amino acid preactivation, external photocatalysts, or transition‐metal catalysts. Herein, a metal‐ and photocatalyst‐free direct decarboxylative amination has been developed through photoactive DAD complexes. This strategy enables efficient access to valuable sulfur‐containing heterocycles, including key intermediates for NEK2 inhibitors and cumene oxidation inhibitors, under mild blue‐light irradiation. Mechanistic studies confirm the formation of a DAD complex, which, upon photoexcitation, undergoes a single‐electron transfer (SET) process to generate radical species, followed by decarboxylation and selective CN coupling. The method features broad substrate scope, operational simplicity, and scalability, providing a practical and sustainable alternative to conventional photocatalytic systems.