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. 2005 Mar 9;127(9):2866-7.
doi: 10.1021/ja0425583.

Catalytic asymmetric synthesis of chiral allylic esters

Stefan F Kirsch  1 , Larry E Overman
Affiliations

Catalytic asymmetric synthesis of chiral allylic esters

Stefan F Kirsch et al. J Am Chem Soc. .

Abstract

Trichloroacetimidate derivatives of prochiral (Z)-2-alken-1-ols react at room temperature with carboxylic acids to give chiral 3-acyloxy-1-alkenes in high enantiopurity in the presence of di-mu-acetatobis[(eta5-(S)-(pR)-2-(2'-(4'-methylethyl)oxazolinyl)cyclopentadienyl,1-C,3'-N)(eta4-tetraphenylcyclobutadiene)cobalt]dipalladium (COP-OAc) or its enantiomer. This reaction has broad scope, proceeds with predictable high stereoinduction, is accomplished at room temperature using high substrate concentrations and low catalyst loadings, and likely proceeds by a novel mechanism.

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Figures

Figure 1
Figure 1
Yield and enantioselectivity in forming (R)-3-acetoxy-1-hexene (4b) using enantiomerically pure palladium(II) complexes under the conditions specified in equation 4
Scheme 1
Scheme 1
Discovery of Palladium-Catalyzed 3-Acyloxy-1-alkene Synthesis
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