Enantioselective Synthesis of α-Alkyl-β,γ-unsaturated Esters through Efficient Cu-Catalyzed Allylic Alkylations

Abstract
A method for enantioselective Cu-catalyzed allylic substitution between various alkylzincs and α,β-unsaturated carboxylic esters that bear a γ-phosphate is reported. These transformations afford α-alkyl-β,γ-unsaturated carbonyls with regioselectivities of 7:1 to >20:1 (SN2‘:SN2) and in 87−97% ee. The utility of the method is illustrated by a convergent total synthesis of topoisomerse II inhibitor (R)-elenic acid.

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