Photoinduced Lignin C α −C β Bond Cleavage and Chemodivergent Functionalization via Iron Catalysis

The photocatalytic conversion of lignin into value‐added chemicals especially those functionalized molecules represent one of the most important strategies for sustainable and environmental‐friendly development. Cleavage of C−C bonds in lignin under mild photocatalytic conditions for refining lignin into useful molecules is meaningful but challenging. Meanwhile, the assembly of diverse functional groups into active lignin fragments during the depolymerization is of great challenging. Herein, using cheap iron catalysts under visible light irradiation, the highly selective and efficient cleavage of C α −C β bond in lignin is realized via ligand‐to‐metal charge transfer (LMCT) and hydrogen atom transfer (HAT) processes. The subsequent divergent functionalization of generated lignin fragment‐based radical intermediates enables an efficient formation of diverse functionalized molecules. This method is also effective for cleavage of C α −C β bond in native lignin, yielding two identified benzaldehyde monomers in a total yield of 8.7 wt %.