Expanding the Pyrimidine Diphosphosugar Repertoire: The Chemoenzymatic Synthesis of Amino- and Acetamidoglucopyranosyl Derivatives

The exploitation of a unique thymidylyltransferase (Ep) allows the rapid syntheses of thymidine and uridine 5′-(aminodeoxy-α-D-hexopyranosyl diphosphates), 5′-(acetamidodeoxy-α-D-hexopyranosyl diphosphates), and even 5′-(aminodideoxy-α-D-hexopyranosyl diphosphates), which are amino analogues of the products from the native reaction of Ep (see scheme).