Total Synthesis of (−)-Okilactomycin

Abstract

A highly convergent synthesis of (-)-okilactomycin is described. Key reactions of this synthesis include a strategy-level diastereoselective oxy-Cope rearrangement/oxidation sequence, a Petasis-Ferrier union/rearrangement tactic, and an efficient RCM reaction to construct the 13-membered macrocyclic ring.

Discovery of okilactomycin and congeners from Streptomyces scabrisporus by antisense differential sensitivity assay targeting ribosomal protein S4

“…20 ) and H-21; and H-9 to H-21 indicated that they were present on the same a-face of the molecule. The NOESY correlations of H-7 to H-5 and H-22 indicated that they were present on the opposite face of the molecule.…”

Synthesis of (−)‐Okilactomycin by a Prins‐Type Fragment‐Assembly Strategy

“…These synthetic efforts culminated in a total synthesis of unnatural enantiomer (−)‐ 1 a and determination of the absolute configuration of the natural product by Smith et al. in 2007 2d,e. There are no syntheses of chrolactomycin ( 1 b ) reported to date.…”

Phorboxazole synthetic studies: design, synthesis and biological evaluation of phorboxazole A and hemi-phorboxazole A related analogues

“…5 ) by condensation of a bis-silylated β-hydroxy acid and an aldehyde, ( B ) olefination utilizing either the Petasis5 or Tebbe6 protocol, and ( C ) Lewis acid-promoted rearrangement of the derived enol ether ( 8 ) to yield the 2,6- cis -disubstituted tetrahydropyranone ( 9 ). In addition to the total synthesis of (+)-phorboxazole A, we have also validated this versatile synthetic tactic for the construction of other complex, biologically active natural products, to include (+)-zampanolide ( 10 ),7 (+)-dactylolide ( 11 ),8 (+)-spongistatin 1 ( 12 ),9 (−)-kendomycin ( 13 ),10 (−)-clavosolide A ( 14 )11 and (−)-okilactomycin ( 15 ) 12…”