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

Philip Freund, Mike Pauls, Daria Babushkina, Thomas Pickl, Christoph Bannwarth, Thorsten Bach

2024Journal of the American Chemical Society59 citationsDOIOpen Access PDF

Abstract

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.

Topics & Concepts

ChemistryHydrogen atomPhotochemistryAtom (system on chip)Organic chemistryGroup (periodic table)Embedded systemComputer scienceFluorine in Organic ChemistrySynthesis and pharmacology of benzodiazepine derivativesChemical Reactions and Mechanisms
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