Microbially Derived P═S and P═Se Bond Formation

Microbial metabolism is a diverse and sustainable source of synthetic reagents that can be programmed for controlled and high-level production via synthetic biology. However, despite the chemical diversity of metabolism, the chemical utility of metabolites, and the available tools to control metabolic chemistry, there remain few examples of the use of cellular metabolites directly for chemical synthesis. Herein, we report that diverse bacteria perform P=S bond formation (Ph₃P to Ph₃PS) via central sulfur metabolism and nonenzymatic chemistry <i>in vivo</i>, which can also be applied to affect microbial P=Se bond formation (Ph₃PSe). To the best of our knowledge, this is the first biochemical and genetic investigation of P=S bond formation in a microbial cell and the first use of microbial metabolites for P=Se bond formation in chemical synthesis.