Total Synthesis and Structural Revision of the Cytotoxin Aruncin B

Org Lett. 2016 Sep 2;18(17):4364-7. doi: 10.1021/acs.orglett.6b02120. Epub 2016 Aug 16.

Abstract

The sodium salts E-15 and Z-15 of the originally proposed dihydropyran acid structure of aruncin B (1) were prepared through ring-closing alkene metathesis (RCM) and ethoxyselenation-selenoxide elimination, but acid sensitivity of these salts, together with inconsistencies in the spectral data, suggested a significant structural misassignment. A β-iodo Morita-Baylis-Hillman reaction to give Z-iodo ester 24, followed by Sonogashira cross-coupling-5-exo-dig lactonization, provided concise access to a Z-γ-alkylidenebutenolide 18, which possessed data corresponding to those originally reported for aruncin B.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Molecular Structure
  • Pyrans / chemical synthesis*
  • Pyrans / chemistry

Substances

  • 2-(8'-ethoxy-8'-methylpropylidene)-5-hydroxy-3,6-dihydro-2H-pyran-4-carboxylic acid
  • Pyrans