Synthesis of (±)-amathaspiramide F: Stereochemical switch of a [2,3]-stevens rearrangement

Arash Soheili, Carrie Johnson, Uttam K. Tambar

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

The total synthesis of complex natural products provides a unique opportunity for learning new lessons in chemical reactivity, which drives the field of synthesis forward. With this goal in mind, we describe our synthetic approach to (±)-amathaspiramide F, a polycyclic alkaloid. The key transformation in our strategy is a tandem palladium-catalyzed allylic amination/[2,3]-Stevens rearrangement, which was recently developed by our lab. Although our retrosynthetic analysis for the amathaspiramides was at first glance straightforward, we uncovered an unusual stereochemical effect that led us down an unexpected path to eventually solve the problem and complete the synthesis of amathaspiramide F. The unexpected diastereoselectivity of the [2,3]-Stevens rearrangement was controlled by the substitution patterns of an aromatic ring. This stereochemical switch may represent a new stereocontrolling element for [2,3]-sigmatropic rearrangements in complex molecular settings.

Original languageEnglish (US)
Title of host publicationStrategies and Tactics in Organic Synthesis
PublisherAcademic Press Inc.
Pages131-154
Number of pages24
ISBN (Print)9780124171855
DOIs
StatePublished - Jan 1 2014

Publication series

NameStrategies and Tactics in Organic Synthesis
Volume10
ISSN (Print)1874-6004

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Keywords

  • Alkaloid
  • Ammonium ylide
  • Diastereoselectivity
  • Palladium
  • [2,3]-rearrangement

ASJC Scopus subject areas

  • Drug Discovery
  • Organic Chemistry

Cite this

Soheili, A., Johnson, C., & Tambar, U. K. (2014). Synthesis of (±)-amathaspiramide F: Stereochemical switch of a [2,3]-stevens rearrangement. In Strategies and Tactics in Organic Synthesis (pp. 131-154). (Strategies and Tactics in Organic Synthesis; Vol. 10). Academic Press Inc.. https://doi.org/10.1016/B978-0-12-417185-5.00006-5