Effective Release of Lignin Fragments from Lignocellulose by Lewis Acid Metal Triflates in the Lignin‐First Approach

Abstract Adding value to lignin, the most complex and recalcitrant fraction in lignocellulosic biomass, is highly relevant to costefficient operation of biorefineries. We report the use of homogeneous metal triflates to rapidly release lignin from biomass. Combined with metal‐catalyzed hydrogenolysis, the process separates woody biomass into few lignin‐derived alkylmethoxyphenols and cellulose under mild conditions. Model compound studies show the unique catalytic properties of metal triflates in cleaving lignin–carbohydrate interlinkages. The lignin fragments can then be disassembled by hydrogenolysis. The tandem process is flexible and allows obtaining good aromatic monomer yields from different woods (36–48 wt %, lignin base). The cellulose‐rich residue is an ideal feedstock for established biorefining processes. The highly productive strategy is characterized by short reaction times, low metal triflate catalyst requirement, and leaving cellulose largely untouched.