Abstract: 8-Hydroxydecanoyl thioester dehydrase is the pivotal enzyme in the biosynthesis of unsaturated fatty acids under anaerobic conditions, catalyzing the equilibration of thioesters of (R)-3-hydroxydecanoic acid,(E)-2-decenoic acid, and (Z)-3-decenoic acid. Substrates chirally labeled with deuterium have been synthesized and incubated with dehydrase. Analysis of labeled products by* H NMR spectroscopy has shown that the pro- ...