jo7b00023_si_001.pdf (10.56 MB)
Download file

Total Synthesis of (−)-Marinisporolide C

Download (10.56 MB)
journal contribution
posted on 20.02.2017, 00:00 by Luiz C. Dias, Emilio C. de Lucca
The first total synthesis of (−)-marinisporolide C is described, which establishes unequivocally the relative and absolute configuration of this oxopolyene macrolide. Key features of this synthesis include a series of highly stereoselective aldol reactions followed by directed reductions to build the polyol domain, a Stille cross-coupling reaction to assemble the polyene, and an intramolecular Horner–Wadsworth–Emmons olefination to forge the macrocyclic ring. Despite the initial approach to marinisporolide A using a Yamaguchi macrolactonization reaction that was unsuccessful due to steric hindrance of the oxygen at the C33 position, we were able to prepare a known derivative of marinisporolide A and consequently confirm its stereochemical assignment.