Organocatalytic Asymmetric Wittig Reactions: Generation of Enantioenriched Axially Chiral Olefins Breaking a Symmetry Plane

Abstract

The first catalytic asymmetric Wittig reaction is presented. Hydrogen-bond donors catalyze the [2+2] cycloaddition reaction between stabilized phosphorus ylides and 4-substituted cyclohexanones, breaking their symmetry plane and furnishing axially chiral olefins with moderate stereoselectivities.

asymmetric catalysis - chirality - olefination - Wittig ­reaction - ylides

References and Notes

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<A NAME="RS04211ST-26">26</A>

We tested 3-phenylcyclobutanone and a 3,4-cis-disubstituted cyclopentanone, using both catalyst 4a and 4g under different reaction conditions. Whereas the cyclopentanone was found to be much less reactive than
4-substituted cyclohexanones, giving the corresponding olefins only in low yields (<20%), the cyclobutanone showed good reactivity, but the alkene was obtained with rather poor enantioselectivity (<36% ee). See the Supporting Information for details.