Herein, the synthesis of 6-deoxygenated α(1→4)-oligoglucans via thermostable α-
glucan phosphorylase (from Aquifex aeolicus VF5)-catalyzed enzymatic chain-elongation is
reported from a maltotriose primer using a non-native substrate, 6-deoxy-α-D-glucose 1-
phosphate. The enzymatic reaction of the two substrates mainly produced a tetrasaccharide
with one 6-deoxy-α-D-glucose unit at the non-reducing end, together with a minor pentasaccharide
with two 6-deoxy-α-D-glucose units. The enzymatic chain-elongation from the primer
in the presence of 6-deoxy-α-D-glucose 1-phosphate and a native substrate, α-D-glucose 1-
phosphate, afforded 6-deoxygenated α(1→4)-oligoglucans with varying degrees of polymerization.
This enzymatic chain-elongation catalyzed by thermostable α-glucan phosphorylase is
an efficient method to produce non-natural oligosaccharides, that is, 6-deoxygenated α(1→4)-
Keywords: 6-Deoxygenated α(1→4)-oligoglucan, enzymatic chain-elongation, α-glucan phosphorylase, glycosylation, non-native substrate,
maltooligosaccharide primer, non-natural oligosaccharide.
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