Application of Lithiation–Borylation to the Total Synthesis of (−)-Rakicidin F

[Image: see text] The stereochemistry of the lipophilic side chain of (+)-rakicidin F had not been determined until recently. Using our lithiation–borylation methodology (“assembly line synthesis”) we were able to efficiently prepare the all-syn isomer as well as the C-21 epimer of the side chain, and comparison with the natural product suggested that the natural product had all-syn stereochemistry. Completion of the total synthesis using a macrolactamization of the northern amide enabled us to confirm Wang and Chen’s stereochemical findings for the structure of (+)-rakicidin F.