Strategies for expanding structural diversity available from olefin isomerization-claisen rearrangement reactions

J Org Chem. 2006 Aug 18;71(17):6397-402. doi: 10.1021/jo0605851.

Abstract

Boron-substituted di(allyl) ethers provide an efficient conduit for expanding the structural diversity available from olefin isomerization-Claisen rearrangement (ICR) reactions. Easily prepared allyl propargyl ethers undergo chemoselective Zr(IV)-catalyzed hydroboration to afford the boron-substituted ICR substrates. The boron-substituted allyl residue undergoes chemoselective Ir(I)-catalyzed olefin isomerization and in situ Claisen rearrangement to afford stereodefined beta-boryl aldehyde products. Functionalization of the C-B linkage by oxidation or Suzuki cross-coupling provides a route to Claisen adducts previously inaccessible from the ICR methodology.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Alkenes / chemistry*
  • Borinic Acids / chemistry
  • Boron / chemistry
  • Crystallography, X-Ray
  • Ethers / chemistry
  • Isomerism
  • Models, Molecular
  • Molecular Structure

Substances

  • Alkenes
  • Borinic Acids
  • Ethers
  • Boron