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Diastereodivergent Behavior of Alkyl versus Cyano Allenylcuprates toward Aldehydes: A Key Role for Lithium

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journal contribution
posted on 20.07.2011, 00:00 by Emmanuel Vrancken, Hélène Gérard, David Linder, Souad Ouizem, Nacira Alouane, Eve Roubineau, Kamel Bentayeb, Jérôme Marrot, Pierre Mangeney
The stereodivergent behavior of allenyl(cyano)- and allenyl(alkyl)cuprates toward aldehydes, providing a selective preparation of both syn- and anti-homopropargylic alcohols, is described. This study, which combines both experimental and theoretical support, shows that the copper nontransferred “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 opens the way to new one-pot synthetic procedures, as illustrated by the combined Klein rearrangement/transmetalation methodology described herein.