Asymmetric claisen rearrangements enabled by catalytic asymmetric Di(allyl) ether synthesis.
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.
Department of Chemistry, University of Pittsburgh, Pennsylvania 15260, USA. sgnelson@pitt.edu
Scott G
SG
Nelson
Kan
K
Wang
D000498:Allyl Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D004987:Ethers / Q000138:chemical synthesis*; D009942:Organometallic Compounds / Q000737:chemistry; D020005:Propanols / Q000737:chemistry; D015032:Zinc / Q000737:chemistry
D000498:Allyl Compounds; D004987:Ethers; D009942:Organometallic Compounds; D020005:Propanols; C006463:allyl alcohol; D015032:Zinc