5.1.3.14 UDP-N-acetyl-alpha-D-glucosamine = UDP-N-acetyl-alpha-D-mannosamine 2-epimerase-catalyzed elimination and readdition of UDP to the glycal intermediate may proceed through a transition state with significant oxocarbenium ion-like character 726555 5.1.3.14 UDP-N-acetyl-alpha-D-glucosamine = UDP-N-acetyl-alpha-D-mannosamine during epimerization, tritium from tritium-enriched water is incorporated into both UDP-N-acetyl-D-glucosamine and UDP-N-acetyl-D-mannosamine 2263 5.1.3.14 UDP-N-acetyl-alpha-D-glucosamine = UDP-N-acetyl-alpha-D-mannosamine mechanism proceeds via cleavage of the anomeric C-O bond, with 2-acetamidoglucal and UDP as enzyme-bound intermediates. It is likely that E1-eliminations via oxocarbenium intermediates are involved in the reaction 2281 5.1.3.14 UDP-N-acetyl-alpha-D-glucosamine = UDP-N-acetyl-alpha-D-mannosamine ordered mechanism, where UDP is the first product released followed by irreversible formation of N-acetyl-mannosamine. A two step mechanism is proposed which involves the elimination of UDP from UDP-N-acetylglucosamine to give a 2-acetamidoglucal intermediate which is subsequently converted to N-acetylmannosamine 2260 5.1.3.14 UDP-N-acetyl-alpha-D-glucosamine = UDP-N-acetyl-alpha-D-mannosamine products: UDP + N-acetyl-D-mannosamine 2257, 2258, 2259, 2260 5.1.3.14 UDP-N-acetyl-alpha-D-glucosamine = UDP-N-acetyl-alpha-D-mannosamine the mechanism involves a trans-elimination of monoprotic UDP to form 2-acetamidoglucal. Followed by a syn-addition, in the direction of UDP-N-acetyl-D-mannosamine formation 2276 5.1.3.14 UDP-N-acetyl-alpha-D-glucosamine = UDP-N-acetyl-alpha-D-mannosamine UDP-N-acetyl-D-mannosamine is not an intermediate 2257, 2258