Recent advances in chemoenzymatic methods: A booming field for asymmetric total synthesis of natural products

The complex chiral architectures of bioactive natural products pose significant challenges for traditional synthesis. The burgeoning field of chemoenzymatic synthesis, which strategically integrates the precision of biocatalysis with the power of synthetic chemistry, has provided conceptual innovations, including modular cascades, de novo identified or engineered enzymes for designed unnatural substrates, and regioselective/enantioselective late-stage oxidations for precise functionalization. This review highlights recent advances (over the past two years) in the asymmetric total synthesis of natural products, showcasing how enantioselective enzymatic reactions are masterfully used for the construction of chiral skeletons or the enantioselective functionalization. Selected case studies span alkaloids, terpenes, and polyketides, underscoring how these chemoenzymatic approaches provide unprecedented levels of efficiency, selectivity, and step economy, thereby streamlining access to complex natural products and influencing significantly on synthetic strategy.