Family 4 Glycosidases Carry Out Efficient Hydrolysis of Thioglycosides by an α,β‐Elimination Mechanism

Thioglycosides are widely used as competitive inhibitors of glycosidases. The first glycosidase capable of hydrolyzing unactivated thioglycosides—BglT, a 6-phospho-β-glucosidase from glucosidase family 4—has been found. The efficient cleavage of the thioglycosidic linkage is a consequence of the α,β-elimination mechanism used by GH4 enzymes, in contrast to the nucleophilic displacement mechanisms of “classical” glycosidases.