Photochemical Deracemization of 4,7-Diaza-1-isoindolinones by Unidirectional Hydrogen Atom Shuttling

High Resolution Image Download MS PowerPoint Slide By coupling a photochemical and a thermal step, a single chiral catalyst can establish a photostationary state in which the enantiopure form of a chiral compound is favored over its racemate. Following this strategy, 3-substituted 4,7-diaza-1-isoindolones were successfully deracemized (74–98% yield, 86–99% ee ) employing 2.5 mol % of a photocatalyst. Key to the success of the reaction is the fact that a chiral benzophenone recruits selectively one enantiomer of the substrate for a photoinduced hydrogen atom transfer. A combination of computational and experimental studies suggests that the hydrogen atom is shuttled via the oxygen atom of the catalyst to the 4-nitrogen atom of the substrate.