Visible-light-mediated metal-free regioselective oxidative C-C bond cleavage of lignin dimers to aromatic acids

The upgrading of lignin is a sustainable and promising pathway for fossil-based aromatic compounds but always faces low selectivity. Herein, a metal-free photocatalyst, 2,4,6-triphenylpyrylium tetrafluoroborate (TPP), was illustrated to remarkably facilitate the regioselective oxidative C alpha-C beta bond cleavage of beta-1 and beta-O-4 lignin alcohol/ketone models into aromatic acids (92-99% yields) under visible-light irradiation at room temperature without any additive/co-catalyst, which was enabled by the synergistic effect of C beta-HMIDLINE HORIZONTAL ELLIPSISC(TPP) interaction and center dot O2-/1O2 species. The synergy of the catalyst-substrate interaction and active species offers a reference for the enhancive and selective transformation of polymeric biomass and complex molecules. The synergy between C beta-HMIDLINE HORIZONTAL ELLIPSISC (TPP) interaction and oxygen-active species enhances oxidative C alpha-C beta bond cleavage of lignin beta-1/beta-O-4 alcohol/ketone models to exclusively afford aromatic acids.