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).