(−)‐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.
The title compound, C16H20O4, was synthesized in the course of the total synthesis of fusaequisin A in order to verify and confirm the configurations of the stereogenic centers and to exclude the possibility of epimerization during the methylation process. The crystal structure of the title compound at 100 K has orthorhombic (P212121) symmetry. The absolute configuration was determined by anomalous dispersion and agrees with the configuration of the allylic alcohol used in the synthesis.
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