Modular polyketide synthases (PKSs) are giant assembly lines that produce an impressive range of biologically active compounds. However, our understanding of the structural dynamics of these megasynthases, specifically the delivery of acyl carrier protein (ACP)‐bound building blocks to the catalytic…
The biosynthesis of the -lactone moiety of the macrolide rhizoxin affords the incorporation of a rare β-branch by Michael addition of a C2 unit to the α,β-unsaturated polyketide intermediate in the branching module (KS-B-ACP). The branching module accepts amine- and carboxamide-substituted substrates…