(A) Proposed LNM biosynthetic pathway featuring LnmKLM-catalyzed β-alkylation of the LnmJ PKS module-8 ACP-tethered intermediate in S. atroolivaceus S-140. (B) Two parallel but distinct pathways for the acyl-S-ACP substrate involved in β-alkylation in polyketide biosynthesis, i.e., acetyl-S-ACP from malonyl-CoA by a dedicated ACP, AT, and KS enzymes and propionyl-S-ACP, from methylmalonyl-CoA by a dedicated ACP and a bifunctional AT/DC enzyme