Reversible natural product glycosyltransferase-catalyzed reactions, compounds and related methods

A method of synthesizing a sugar moiety A-nucleotide diphosphate, in-situ, from a biomolecule having a sugar moiety A, the method comprising the steps of:

• (a) incubating the biomolecule having the sugar moiety A with a nucleotide diphosphate in the presence of a glycosyltransferase capable of glycosylating the biomolecule that is selected from the group consisting of Micromonospora echinospora calicheamicin glycosyltransferase 1 (CalG1), Micromonospora echinospora calicheamicin glycosyltransferase 2 (CalG2), Micromonospora echinospora calicheamicin glycosyltransferase 3 (CalG3), Micromonospora echinospora calicheamicin glycosyltransferase 4 (CalG4), Amycolatopsis orientalis glycosyltransferase D (GtfD), Amycolatopsis orientalis glycosyltransferase E (GtfE), Saccharopolyspora erythraea erythromycin glycosyltransferase BV (EryBV), and Streptomyces avermitilis avermectin glycosyltransferase (AveBI), wherein the sugar moiety A in the biomolecule is excised from the biomolecule, thereby generating the sugar moiety A-nucleoside diphosphate and a biomolecule aglycon;
• and
• (b) isolating the sugar moiety A-nucleotide diphosphate from step (a),
• wherein the biomolecule is an enediyne, a vancomycin, a bleomycin, an anthracycline, a macrolide, a pluramycin, an aureolic acid, an indolocarbazole, an aminglycoside, a glycopeptide, a polyene, a coumarin, a benzoisochromanequinone, a calicheamicin, an erythromycin, an avermectin, an ivermectin, an angucycline, a cardiac glycoside, a steroid or a flavinoid.