Chemoenzymatic Synthesis of the Antifungal Compound (–)‐Pestynol by a Convergent, Sonogashira Construction of the Central Yne‐Diene

A total synthesis of the fungal‐derived natural product pestynol is reported via a convergent chemoenzymatic approach from the readily available precursors geranyl bromide, ethyl acetoacetate, trimethylsilylacetylene, and bromobenzene. Synthetic (–)‐pestynol proved to be identical in all respects to the natural material, allowing confirmation of the structure including absolute stereochemistry.