Expanding the pyrimidine diphosphosugar repertoire: The chemoenzymatic synthesis of amino- and acetamidoglucopyranosyl derivatives

The exploitation of a unique thymidylyltransferase (E _p) 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 E _p (see scheme).