Regioselective thexyldimethylsilylation of (1➔3)-glucans - Does the linkage type matter

α- and β-(1➔3)-linked polysaccharides dissolved in N,N-dimethyl acetamide (DMA) were subjected to conversion with thexyldimethylchlorosilane (TDMS-Cl) in presence of pyridine as base. A degree of substitution of TDMS groups (DS_Si) between 0.7 and 1.0 was achieved indicating that the β-(1➔3)-linked curdlan (DS_Si 0.7) is less reactive than α-(1➔3)-linked glucans (DS_Si ca. 1). The synthesis sequence of permethylation, desilylation, and acetylation afforded the corresponding acetyl-methyl derivatives, where unaffected OH groups were methylated and TDMS groups were replaced by acetyl moieties. NMR spectroscopic investigations revealed a highly selective silylation of the primary OH group at position 6 while leaving the secondary OH moieties unaffected. This pronounced selectivity was found to be distinctly higher compared to cellulose and starch. Conversion of (1➔4)-linked polysaccharides dissolved in DMA/LiCl with TDMS-Cl leads to products consisting of both 6-mono-O- and 2,6-di-O- silylated repeating units. Regioselective 6-mono-O-silylation requires the hazardous use of liquid ammonia.