Abstract

The so-called γ-TTSA method has been developed for the cleavage of β-O-4 linkages in lignin. It consists of four steps: (1) γ-tosylation, (2) thioetherification (substitution reaction with 1-dodecanethiol to γ-thioether), (3) sulfonylation (oxidation from γ-thioether to γ-sulfone), and (4) mild alkali degradation of γ-sulfone. The method was tested on non-phenolic dimeric β-O-4 lignin model compounds: 1G (4-benzyloxy-3-methoxyphenylglycerol-β-guaiacyl ether), 1S (4-benzyloxy-3,5-dimethoxyphenylglycerol-β-syringyl ether), and 1H (4-benzyloxyphenylglycerol-β-phenyl ether). It is demonstrated that the mild alkali degradation of the γ-sulfone group proceeds efficiently, i.e., the electron-withdrawing sulfone group at γ-position contributes to the cleavage of β-O-4 linkages. The γ-TTSA method may be especially useful for the elucidation of lignin-carbohydrate complex structures containing benzylether bonds.