Toward a total synthesis of amphidinolide X and Y. The tetrahydrofuran-containing fragment C12-C21

Org Lett. 2007 Mar 15;9(6):989-92. doi: 10.1021/ol063035y. Epub 2007 Feb 13.

Abstract

The key THF derivative (9a) for an enantioselective synthesis of amphidinolide X/Y was obtained from 1a via a selenoetherification reaction. In fact, among the cyclization methods investigated, the highest yield and stereocontrol were achieved at -78 degrees C with PhSeCl/EtiPr2N from diols 1a (anti-Z) and 1b (anti-E) and with PhSeCl/ZnBr2 from diols 1c (syn-Z) and 1d (syn-E). Also, surprisingly, use of protecting groups (on the allylic OH) was detrimental in the cases studied. The diverse THF-tetrasubstituted stereoisomers will provide a series of amphidinolide X/Y analogues. [structure: see text]

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bromides / chemistry
  • Catalysis
  • Cyclization
  • Furans / chemistry*
  • Macrolides / chemical synthesis*
  • Models, Chemical
  • Organoselenium Compounds / chemistry
  • Stereoisomerism
  • Zinc Compounds / chemistry

Substances

  • Bromides
  • Furans
  • Macrolides
  • Organoselenium Compounds
  • Zinc Compounds
  • amphidinolide X
  • amphidinolide Y
  • tetrahydrofuran
  • zinc bromide