Abstract The stereoselective total synthesis of an antiproliferative and antifungal α ‐pyrone natural product (6 S )‐5,6‐dihydro‐6‐[(2 R )‐2‐hydroxy‐6‐phenylhexyl]‐2 H ‐pyran‐2‐one is described. The key steps involved are the Prins cyclization, Mitsunobu reaction, and ring‐closing metathesis reaction.