Enantioselective synthesis of alpha-alkyl-beta,gamma-unsaturated esters through efficient cu-catalyzed allylic alkylations

Kerry E Murphy; Amir H Hoveyda

doi:10.1021/ja0300618

Enantioselective synthesis of alpha-alkyl-beta,gamma-unsaturated esters through efficient cu-catalyzed allylic alkylations

J Am Chem Soc. 2003 Apr 23;125(16):4690-1. doi: 10.1021/ja0300618.

Authors

Kerry E Murphy¹, Amir H Hoveyda

Affiliation

¹ Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.

PMID: 12696870
DOI: 10.1021/ja0300618

Abstract

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.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, U.S. Gov't, P.H.S.

MeSH terms

Alkylation
Allyl Compounds / chemical synthesis*
Allyl Compounds / chemistry
Copper / chemistry*
Esters / chemical synthesis*
Organometallic Compounds / chemistry
Stereoisomerism
Zinc / chemistry

Substances

Allyl Compounds
Esters
Organometallic Compounds
Copper
Zinc

Grants and funding

GM-47480/GM/NIGMS NIH HHS/United States