Photoexcited Palladium-Initiated Remote Desaturation of N -Alkoxypyridinium Salts.

1,5-Hydrogen atom transfer (HAT) is an effective strategy to achieve remote desaturation of nonfunctionalized alkanes. Herein, we report a photoinduced remote desaturation reaction of N -alkoxypyridinium salts, which serve as alkoxyl radical precursors. Mechanistic studies show that a single electron transfer between the excited palladium complex and a N -alkoxypyridinium salt initiates a radical chain process leading to desaturation of N -alkoxypyridinium salts. This chain mechanism is supported by the measurement of the quantum yield of this reaction (Φ = 82). This reaction is applicable to a range of N -alkoxypyridinium salts, including some complex molecule-derived ones.