Mechanistic Insight into Enzymatic Glycosyl Transfer with Retention of Configuration through Analysis of Glycomimetic Inhibitors

Structural “valid”‐ation: The mechanism of enzyme‐catalyzed glycosyl transfer with retention of anomeric configuration continues to baffle, a situation compounded by the lack of insightful 3‐D structures of ternary enzyme complexes. Synthesis and multi‐dimensional kinetic analysis of validoxylamine derivatives are used to access the 3‐D structure of a ternary complex (see picture; U=uridyl) providing insight into the geometry and donor–acceptor interplay at the glycosyltransfer site.