The alkaline cleavage of β-ether bonds of phenolic lignin model compounds by reducing sugars has been shown to occur by the reaction of the quinone methide of the lignin model with a sugar-derived enediol. Reaction of the quinone methide of 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)ethanol with L-ascorbic acid in the absence of base gives a carbon-carbon bonded intermediate formed by reaction of the C-2 carbon of the ascorbic acid enediol with the α-carbon of the quinone methide. This intermediate then fragments under alkaline conditions to guaiacol and vinylguaiacol, the same products as obtained from heating the β-ether itself with ascorbic acid or reducing sugars under alkaline conditions. The isolated intermediate was obtained as a one to one mixture of two stereoisomers, isomeric at the benzylic carbon, from which one isomer was selectively crystallised. The generality of the reaction and its relevance to the development of alternative pulping processes is discussed and the possibility of carbon-carbon bonded lignin carbohydrate complexes being formed via enediols is suggested.