1 Introduction Fatty acyl-coenzyme A (CoA) thioesters occupy a central position in cellular metabolism, functioning as activated electrophiles that participate in fatty acid biosynthesis, β-oxidation, and the assembly of complex natural products such as polyketides [1] and nonribosomal peptides (Figure 1) [2]. Beyond their native biological roles, acyl-CoAs have emerged as valuable intermediates for the sustainable production of biofuels [3, 4], green chemicals [5], and pharmaceuticals [3, 6].