Formal intramolecular photoredox chemistry of anthraquinones in aqueous solution: photodeprotection for alcohols, aldehydes and ketones

Abstract

The formal intramolecular photoredox reaction initially discovered for the parent 2-(hydroxymethyl)anthraquinone (1) in aqueous solution has been extended to a variety of anthraquinones derivatives 6–13, to explore the generality of the reaction, and to investigate its potential utility as a photodeprotecting chromophore. In addition, the related diketone 14 was studied to investigate the need for the anthraquinone chromophore in these formal intramolecular reactions. All the anthraquinones studied (except for 9) undergo formal unimolecular photoredox reaction with a range of quantum yields (Φ = 0.02–0.7). Anthraquinones 7, 8, 10 and 11 photoreleased the corresponding alcohol, aldehyde, or ketone with good yields (80–90%), making it potentially useful for photocaging in aqueous solution. Diketone 14 undergoes an analogous photoredox reaction but only in acid (Φ = 0.003, pH < 1), to give the formal redox product diphenylisobenzofuran 32 thereby demonstrating that other aromatic diketones can react in an analogous fashion. The ionic photochemistry exhibited by these aromatic ketones is fully compatible with the recent discovery of the surprising acid-catalyzed photochemical hydration of benzophenone reported by Jacob Wirz and coworkers (M. Ramseier, P. Senn and J. Wirz, J. Phys. Chem. A, 2003, 107, 3305–3315).