Solving the Structural Puzzles of Amipurimycin and Miharamycins Enabled by Stereodivergent Total Synthesis.

The efforts toward the synthesis of amipurimycin and miharamycin A/B, two peptidyl nucleoside antibiotics bearing a unique nine carbon C3-branched pyranosyl amino acid core, are accounted. Highlighted is our stereodivergent total synthesis of all the possible diastereoisomers of amipurimycin, which has enabled us to solve the structural puzzles of amipurimycin and miharamycin A/B after ∼50 years of their discovery.