Enantioselective synthesis of alpha-alkyl-beta,gamma-unsaturated esters through efficient cu-catalyzed allylic alkylations.
A method for enantioselective Cu-catalyzed allylic substitution between various alkylzincs and alpha,beta-unsaturated carboxylic esters that bear a gamma-phosphate is reported. These transformations afford alpha-alkyl-beta,gamma-unsaturated carbonyls with regioselectivities of 7:1 to >20:1 (S(N)2':S(N)2) and in 87-97% ee. The utility of the method is illustrated by a convergent total synthesis of topoisomerse II inhibitor (R)-elenic acid.
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 / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D004952:Esters / Q000138:chemical synthesis*; D009942:Organometallic Compounds / Q000737:chemistry; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry
D000498:Allyl Compounds; D004952:Esters; D009942:Organometallic Compounds; D003300:Copper; D015032:Zinc