A solvent‐, transition‐metal‐, and base‐free organocatalytic system (Ph 3 CBr or TMSI) enables efficient O‐ to N‐migration for N‐alkylated pyridone synthesis. Critically, gram‐scale production of a cinnamyl‐derived product (4.73 mmol) completes within 3 h at 100°C without yield erosion. Stereospecific 1,3‐rearrangements predominantly preserve alkene geometry, while resultant pyridones exhibit tunable fluorescence (Φ up to 0.39 in chloroform). This protocol establishes an eco‐compatible, directly amplifiable platform toward functional heterocycles.
Yan et al. (Tue,) studied this question.