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. 2008 Oct 2;10(19):4387-9.
doi: 10.1021/ol801931v. Epub 2008 Sep 5.

Simple chiral diene ligands provide high enantioselectivities in transition-metal-catalyzed conjugate addition reactions

Kazuhiro Okamoto  1 , Tamio Hayashi, Viresh H Rawal
Affiliations

Simple chiral diene ligands provide high enantioselectivities in transition-metal-catalyzed conjugate addition reactions

Kazuhiro Okamoto et al. Org Lett. .

Abstract

Chiral dienes possessing the bicyclo[2.2.2]octadiene framework were prepared readily through the [4 + 2] cycloaddition of ( R)-alpha-phellandrene with methyl propiolate as the key step. Diene 9, substituted with a tertiary alcohol on one of the two double bonds, is prepared in just one step from the cycloadduct and is highly effective as a chiral ligand for rhodium-catalyzed asymmetric conjugate addition reactions, giving the corresponding addition products with higher enantioselectivity than other chiral dienes.

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Figures

Figure 1
Figure 1
Chiral Diene Ligands for Catalytic Asymmetric Reactions
Figure 2
Figure 2
Stereochemical Pathway with Rh/(R,R,R)-9.
Scheme 1
Scheme 1
Synthesis of Chiral Dienes
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