Borate‐Mediated Stereo‐ and Topo‐Selective Methylation of 1,4‐β‐Glucomannan

Abstract

Konjak glucomannan (KGM) is methylated with NaOH/MeI in water in the presence of borate and as a reference without this additive. With increasing equiv. of borate increasing suppression of 2‐ and 3‐O‐methylation of mannosyl residues (M) is observed, while glucosyl units (G) are mainly affected at O‐6, but to much lower extent. Raising the temperature and/or addition of acetone as a co‐solvent enhance reactivity, but at the cost of M/G regioselectivity. O‐Methyl konjac glucomannans (M‐KGM) with an average degree of substitution (DS) up to 0.8 and a DS ratio for G and M up to 2 are obtained. From liquid chromatrography–electrospray ionization–mass spectrometry (LC‐ESI‐MS) of the oligosaccharides obtained from M‐KGM, it is concluded that borate‐mediated transient protection might also depend on the location of M within KGM. Comparison with random and block models supports random distribution of M and G in KGM. Thermogravimetric analysis shows higher decomposition temperature of M‐KGMs with increasing DS.