Strategies for expanding structural diversity available from olefin isomerization-claisen rearrangement reactions.
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.
Stevens
Benjamin D
BD
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
Bungard
Christopher J
CJ
Nelson
Scott G
SG
D000475:Alkenes / Q000737:chemistry*; D001889:Borinic Acids / Q000737:chemistry; D001895:Boron / Q000737:chemistry; D018360:Crystallography, X-Ray; D004987:Ethers / Q000737:chemistry; D007536:Isomerism; D008958:Models, Molecular; D015394:Molecular Structure
D000475:Alkenes; D001889:Borinic Acids; D004987:Ethers; D001895:Boron