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Synlett 2011(18): 2745-2749  
DOI: 10.1055/s-0031-1289516
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Lucia Gramignaa, Sara Ducea,b, Giacomo Filippinia, Mariafrancesca Fochia, Mauro Comes Franchinia, Luca Bernardi*a
a Department of Organic Chemistry ‘A. Mangini’, University of Bologna, Viale Risorgimento 4, 40136 Bologna, Italy
Fax: +39(051)2093654; e-Mail: luca.bernardi2@unibo.it;
b Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco 28049, Madrid, Spain
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Publikationsverlauf

Received 16 May 2011
Publikationsdatum:
06. Oktober 2011 (online)

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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.

Key words

asymmetric catalysis - chirality - olefination - Wittig ­reaction - ylides

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26

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.