Catalyzed olefin isomerization leading to highly stereoselective Claisen rearrangements of aliphatic allyl vinyl ethers.
Iridium(I)-catalyzed olefin isomerization in bis(allyl) ethers is integrated into a generally applicable strategy for affecting highly stereoselective Claisen rearrangements. Catalyzed alkene isomerization affords allyl vinyl ethers from easily prepared di(allyl) ethers; direct thermolysis of these reaction mixtures leads to highly diastereoselective [3,3] sigmatropic rearrangements affording syn-2,3-dialkyl-4-pentenal derivatives. An easily executed strategy for realizing asymmetric variants of the isomerization-Claisen rearrangement (ICR) reactions is also described.
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA. sgnelson@pitt.edu
Scott G
SG
Nelson
Christopher J
CJ
Bungard
Kan
K
Wang
D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D007495:Iridium / Q000737:chemistry; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry*
D000447:Aldehydes; D000475:Alkenes; D000498:Allyl Compounds; D014753:Vinyl Compounds; C100195:vinyl ether; D007495:Iridium