Simultaneous Generation of Methyl Esters and CO in Lignin Transformation

Lignin is an abundant renewable carbon source. Due to its complex structure, utilization of lignin is very challenging. Herein, we describe an efficient strategy for the simultaneous utilization of lignin, in which the methoxy groups in lignin react with carboxylic acids to generate methyl carboxylates and the other alkyl and phenyl carbons react with oxygen to predominantly form CO that can be used directly in carbonylation reactions. The method was applied to the methylation of various functionalized aryl and alkyl carboxylic acids, including natural compounds, to produce valuable chemicals, including pharmaceuticals. No solid or liquid residues remain after the reaction. Mechanistic studies demonstrate that a well‐ordered C−C and C−O bond activation sequence takes place to realize total transformation of lignin. This work opens a way for transformation of the entire lignin polymer into valuable products, exemplified by the synthesis of the pharmaceutical, Ramipril, on a gram scale.