Total synthesis of (+)-roxaticin via C-C bond forming transfer hydrogenation: a departure from stoichiometric chiral reagents, auxiliaries, and premetalated nucleophiles in polyketide construction

J Am Chem Soc. 2010 Nov 10;132(44):15559-61. doi: 10.1021/ja1082798.

Abstract

A total synthesis of the oxo-polyene macrolide (+)-roxaticin is achieved in 20 steps from 1,3-propanediol. In this approach, 9 of 10 C-C bonds formed in the longest linear sequence are made via metal catalysis, including 7 C-C bonds formed by iridium catalyzed alcohol C-C coupling. Notably, the present synthesis, which represents the most concise preparation of any oxo-polyene macrolide reported to date, is achieved in the absence of chiral reagents and chiral auxiliaries with minimal use of premetalated C-nucleophiles.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Hydrogenation
  • Iridium / chemistry
  • Macrolides / chemical synthesis
  • Macrolides / chemistry*
  • Molecular Structure
  • Stereoisomerism

Substances

  • Macrolides
  • roxaticin
  • Iridium