The plecomacrolildes are unusual macrocyclic secondary metabolites that are produced by different Streptomyces species and have received considerable medicinal, as well as synthetic interest.  Key examples include the bafilomycins, formamicinone, and elaiolide. Our laboratory has focused on a reiterative methodology for the synthesis of polypropionates based on epoxide chemistry that has shown success in the assembly of several fragments, including the C14�C25 bafilomycin A1 polypropionate chain.  This approach was extended to the syntheses of the C12�C16 and C20�C24 fragments of elaiolide and formamicinone, respectively. These transformations include regioselective cleavage of trans-epoxides with alkynyl aluminum reagents and diastereoselective epoxidation of homoallylic alcohols. An Ireland-Claisen rearrangement generates a ?,d-unsaturated acid that, upon iodolactonization/methanolysis, yields the required syn-anti configuration for both fragments.  These variations have enabled a general methodology for the synthesis of the polypropionate chain included in the plecomacrolide family. Supported by NIH-RISE (1R25-GM-61151-01A1) and NIH-SCORE (2S06GM-08102-29).

General epoxide-based methodology for the synthesis of the hemiacetal rings in the plecomacrolide family

243rd National Meeting (2012)

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