Evolution of the total synthesis of (-)-okilactomycin exploiting a tandem oxy-cope rearrangement/oxidation, a Petasis-Ferrier union/rearrangement, and ring-closing metathesis

J Am Chem Soc. 2009 Feb 18;131(6):2348-58. doi: 10.1021/ja8084669.

Abstract

An effective, asymmetric total synthesis of the antitumor antibiotic (-)-okilactomycin (1), as well as assignment of the absolute configuration, has been achieved exploiting a convergent strategy. Highlights of the synthesis include a diastereoselective oxy-Cope rearrangement/oxidation sequence to install the C(1) and C(13) stereogenic centers, a Petasis-Ferrier union/rearrangement to construct the highly functionalized tetrahydropyranone inscribed within the 13-membered macrocycle ring, employing for the first time a sterically demanding acetal, an intramolecular chemoselective acylation to access an embedded bicyclic lactone, and an efficient ring-closing metathesis (RCM) reaction to generate the macrocyclic ring.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Acetals / chemistry
  • Aldehydes / chemical synthesis
  • Aldehydes / chemistry
  • Cyclization
  • Lactones / chemical synthesis
  • Macrocyclic Compounds / chemical synthesis
  • Oxidation-Reduction
  • Pyrans / chemical synthesis
  • Pyrans / chemistry
  • Stereoisomerism
  • Streptomyces / chemistry

Substances

  • Acetals
  • Aldehydes
  • Lactones
  • Macrocyclic Compounds
  • Pyrans
  • okilactomycin