Total Enantioselective Synthesis of the Endophytic Fungal Polyketide Phomolide H and Its Structural Revision

A total synthesis of the proposed structure of the natural polyketide‐macrolactone phomolide H 2 has been achieved following a bidirectional strategy from l ‐tartaric acid. The originally assigned structure of phomolide H displayed discordant NMR spectroscopic data in comparison with synthetic 2 . The synthetic strategy was extended to prepare diastereomers and epimeric methyl‐ethers of the natural product, structural analysis of which revealed a match of the natural product with diastereomer 27 . The structural revision of phomolide H from 2 to the methanol solvate of compound 27 is presented.