Asymmetric photooxidation of glycerol to hydroxypyruvic acid over Rb-Ir catalytic pairs on poly(heptazine imides).

Selective asymmetric oxidation of glycerol (GLY) to hydroxypyruvic acid (HPA) offers an attractive approach for chiral drug synthesis, but this process is highly challenging. Here we develop a photocatalytic method to achieve heterogeneous selective photooxidation of GLY to HPA over rubidium (Rb) and iridium (Ir) catalytic pairs decorated on a poly(heptazine imide) framework. The Rb sites effectively adsorb GLY molecules through the terminal -OH groups, thus inhibiting their oxidation during photoreaction, while the Ir sites enhance the oxygen reduction reaction and the in situ generated surficial oxygen-reduction radicals on Ir can protect the reactive C-centred radical intermediates produced during photooxidation. The spatial arrangement of Rb and Ir sites facilitates hydrogen extraction-an essential rate-determining step for GLY photooxidation-and protects C3 radical intermediates from overoxidation. This photocatalytic system achieves a remarkable productivity for HPA synthesis (~8,000 μmol of HPA per gram of photocatalyst per hour) under visible-light illumination.