Photodecarboxylation of Xanthone Acetic Acids:  C−C Bond Heterolysis from the Singlet Excited State

Abstract

[reaction: see text] Irradiation of 2- and 4-xanthone acetic acid in aqueous buffer (pH 7.4) leads to efficient (Phi = 0.67 and 0.64, respectively) photodecarboxylation to give the corresponding methyl products, consistent with an intermediate benzylic carbanion. Fluorescence and laser flash photolysis (LFP) studies suggest singlet state reactivity, which is unusual for aromatic ketones. 3-Xanthone acetic acid is photoinert under the same conditions. The results suggest that the reactive xanthone acetic acids are promising precursors for carbanion-mediated photocages.