Tunable C-H Functionalization and Dearomatization Enabled by an Organic Photocatalyst

C-H functionalization and dearomatization constitute fundamental transformations of aromatic compounds, which find wide applications in various research areas. However, achieving both transformations from the same substrates with a single catalyst by operating a distinct mechanism remains challenging. Here, we report a photocatalytic strategy to modulate the reaction pathways that can be directed toward either C-H functionalization or dearomatization under redox-neutral or net-reductive conditions, respectively. Two sets of indoles and indolines bearing tertiary alcohols are divergently furnished with good yields and high selectivity. The key to success is the introduction of isoazatruxene ITN-2 as a novel photocatalyst (PC), which outperforms the commonly used PCs. The ready synthesis and high modulability of isoazatruxene type PCs indicate their great application potential. Starting from the same substrates, tunable C-H functionalization and dearomatization have been achieved under the catalysis of a new organic photocatalyst - isoazatruxene ITN-2.