A Hyaluronidase Supercatalyst for the Enzymatic Polymerization to Synthesize Glycosaminoglycans

Hyaluronidase (HAase) catalyzes multiple enzymatic polymerizations with controlling regio‐ and stereoselectivity perfectly. This behavior, that is, the single enzyme being effective for multireactions and retaining the enzyme catalytic specificity, is not usual, and hence, HAase is a supercatalyst. Various sugar oxazoline monomers prepared based on the concept “transition‐state analogue substrate” were successfully polymerized and copolymerized with HAase catalysis, yielding natural and unnatural glycosaminoglycans. Absolutely super! A hyaluronidase supercatalyst induces enzymatic polymerization and copolymerization of various sugar oxazoline monomers designed on the basis of the “transition‐state analogue substrate” concept, providing a variety of glycosaminoglycans (an example is shown here). All reactions proceed under total control of regioselectivity and stereochemistry.