Asymmetric claisen rearrangements enabled by catalytic asymmetric Di(allyl) ether synthesis
1Department of Chemistry, University of Pittsburgh, Pennsylvania 15260, USA. sgnelson@pitt.edu
Abstract:
Merging the catalytic asymmetric synthesis of di(allyl) ethers with ensuing olefin isomerization-Claisen rearrangement (ICR) reactions provides a convenient, two-step route to asymmetric aliphatic Claisen rearrangements from easily obtained starting materials. These reactions deliver the 2,3-disubstituted 4-pentenal derivatives characteristic of aliphatic Claisen rearrangements with excellent relative and absolute stereocontrol. A catalytic enantioselective synthesis of the (+)-calopin dimethyl ether demonstrates the utility of this reaction technology in asymmetric synthesis enterprises.
Related Concept Videos
Intramolecular Claisen Condensation of Dicarboxylic Esters: Dieckmann Cyclization
β-Dicarbonyl Compounds via Crossed Claisen Condensations
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Esters to β-Ketoesters: Claisen Condensation Mechanism
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement


