A formal synthesis of (-)-cyanolide A featuring a stereoselective Mukaiyama aldol reaction and oxocarbenium reduction

J Org Chem. 2011 Oct 7;76(19):8027-32. doi: 10.1021/jo201210u. Epub 2011 Sep 1.

Abstract

The formal synthesis of the marine natural product (-)-cyanolide A is presented. The synthetic strategy is centered on two acyclic diastereoselective reactions and a single cyclic reaction with modest to excellent dr based on an initial stereocenter. Most notable is a highly stereoselective oxocarbenium reduction based on a "mismatched" reactive conformer to afford the β-C-glycoside subunit leading to an efficient synthesis of the diolide aglycon in 12 overall steps.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Aldehydes / chemistry*
  • Carbon / chemistry*
  • Chemistry Techniques, Synthetic / methods*
  • Macrolides / chemical synthesis*
  • Macrolides / chemistry*
  • Oxidation-Reduction
  • Stereoisomerism
  • Substrate Specificity

Substances

  • Aldehydes
  • Macrolides
  • cyanolide A
  • Carbon
  • 3-hydroxybutanal