Catalytic enantioselective synthesis of quaternary all-carbon stereogenic centers. Preparation of alpha,alpha'-disubstituted beta,gamma-unsaturated esters through Cu-catalyzed asymmetric allylic alkylations.
[reaction: see text] Peptide-based chiral ligands, readily prepared from commercially available materials, are used to promote Cu-catalyzed asymmetric allylic alkylations of alpha,beta-unsaturated esters bearing a gamma-phosphate with various alkylzinc reagents. These transformations lead to the formation of alpha,alpha'-dialkyl-beta,gamma-unsaturated esters in high yields as well as high regio- (re) and enantioselectivities (ee).
Murphy
Kerry E
KE
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Hoveyda
Amir H
AH
D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D004952:Esters; D006838:Hydrocarbons / Q000138:chemical synthesis*; D013237:Stereoisomerism
D000498:Allyl Compounds; D004952:Esters; D006838:Hydrocarbons; D003300:Copper