Visible‐Light‐Driven Heterocyclic Fluoroalkylation Via Electron Donor−Acceptor Complexes

Abstract Heterocyclic fluoroalkylation is initiated through a photochemical reaction involving an electron donor–acceptor complex. The reaction proceeds smoothly without requiring a photocatalyst, transition metal catalyst or additional oxidant. Through extensive experiments, we optimised the heterocyclic fluoroalkylation method and confirmed its versatility and effectiveness on various substrates. The process synthesises fluoroalkylated quinoxalinones and indolones with high efficiency and was successfully extended to gram‐scale applications, highlighting its practical utility. Detailed mechanistic analyses, supported by density functional theory calculations elucidated the role of the electron donor–acceptor complexes and deciphered the distinct radical chain reaction mechanism inherent in the halogen‐atom transfer pathway. Given the importance of fluoroalkyl groups in pharmaceuticals, this simple and efficient method promises substantial applications in medicinal chemistry and materials science.