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Catalyzed Olefin Isomerization Leading to Highly Stereoselective Claisen Rearrangements of Aliphatic Allyl Vinyl Ethers

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journal contribution
posted on 29.10.2003 by Scott G. Nelson, Christopher J. Bungard, Kan Wang
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.