Sequencing of three-component olefin metatheses: total synthesis of either (+)-gigantecin or (+)-14-deoxy-9-oxygigantecin

Org Lett. 2006 Jul 20;8(15):3383-6. doi: 10.1021/ol061383u.

Abstract

[Structure: see text] An efficient, flexible, and highly convergent strategy for accessing skipped bis-THF containing Annonaceous acetogenins is demonstrated by the synthesis of each of (+)-gigantecin (1) and its constitutional isomer (+)-14-deoxy-9-oxygigantecin (11). The skeleton of each compound is produced, at will, from the same precursors via a three-component ring-closing/cross-metathesis sequence that differs only in the ordering of the RCM vs CM events. Another notable aspect is the use of in situ epoxide-closing and -opening of iodohydrins with dimethylsulfonium methylide to provide inverted allylic alcohols.

Publication types

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

MeSH terms

  • Alkenes / chemistry
  • Annonaceae / chemistry
  • Antineoplastic Agents, Phytogenic / chemical synthesis*
  • Antineoplastic Agents, Phytogenic / chemistry
  • Antineoplastic Agents, Phytogenic / pharmacology
  • Furans / chemical synthesis*
  • Furans / chemistry
  • Furans / pharmacology
  • Lactams
  • Lactones / chemical synthesis*
  • Lactones / chemistry
  • Lactones / pharmacology
  • Molecular Structure
  • Stereoisomerism

Substances

  • 14-deoxy-9-oxygigantecin
  • Alkenes
  • Antineoplastic Agents, Phytogenic
  • Furans
  • Lactams
  • Lactones
  • gigantecin