Total Synthesis and Structural Assignment of (−)‐Fusaequisin A

(−)‐Fusaequisin A is an irregularly assembled polyketide isolated from the ascomycete Fusarium equiseti. Fusaequisin A shares a carbon backbone with curvicollide C from the ascomycete Podospora curvicolla but its absolute configuration remained hitherto unsettled. Herein, we document the total synthesis of (−)‐fusaequisin A and its 4‐O‐desmethyl derivative following a central‐to‐lateral building block strategy. Catalytic asymmetric Claisen rearrangement, Julia‐Kocienski olefination and olefin cross‐metathesis served as key C/C‐connecting transformations. The constitution and absolute configuration of (−)‐fusaequisin A was deduced and the original structural assignment was adjusted.