Diastereodivergent Behavior of Alkyl- versus Cyano- Allenylcuprates towards Aldehydes: a Key Role for Lithium - Institut Parisien de Chimie Moléculaire Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2011

Diastereodivergent Behavior of Alkyl- versus Cyano- Allenylcuprates towards Aldehydes: a Key Role for Lithium

Résumé

The stereodivergent behavior of allenyl(cyano)- and allenyl(alkyl)- cuprates toward aldehydes, providing a selective preparation of both syn or anti homopropargylic alcohols, is described. This study, which combines both experimental and theoretical support, shows that the copper non-transferred "dummy ligand" controls the localization of the lithium cation with respect to the allenylcuprate moiety. As a consequence, Li+ acts as a Lewis acid activator but also controls the diastereoselectivity during the addition of allenylcuprates onto aldehydes. The combined high selectivity, efficiency and versatility of these cuprate compounds open the way to new one-pot synthetic procedures as illustrated by the combined Klein rearrangement / transmetallation methodology described herein.

Domaines

Chimie organique
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Dates et versions

hal-00605979 , version 1 (05-07-2011)

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Emmanuel Vrancken, Hélène Gérard, David Linder, Ouizem Souad, Nacira Alouane, et al.. Diastereodivergent Behavior of Alkyl- versus Cyano- Allenylcuprates towards Aldehydes: a Key Role for Lithium. Journal of the American Chemical Society, 2011, ⟨10.1021/ja200702a⟩. ⟨hal-00605979⟩
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