Diastereodivergent Behavior of Alkyl- versus Cyano- Allenylcuprates towards Aldehydes: a Key Role for Lithium
| Autor: | David Linder, Pierre Mangeney, Kamel Bentayeb, Jérôme Marrot, Nacira Alouane, Eve Roubineau, Hélène Gérard, Emmanuel Vrancken, Souad Ouizem |
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| Přispěvatelé: | Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire de chimie théorique (LCT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique (CO), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2011 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry [CHIM.ORGA]Chemical Sciences/Organic chemistry chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences Colloid and Surface Chemistry chemistry Organic chemistry Lithium Alkyl |
| Zdroj: | Journal of the American Chemical Society Journal of the American Chemical Society, American Chemical Society, 2011, ⟨10.1021/ja200702a⟩ Journal of the American Chemical Society, 2011, ⟨10.1021/ja200702a⟩ |
| ISSN: | 0002-7863 1520-5126 |
| DOI: | 10.1021/ja200702a⟩ |
| Popis: | International audience; 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. |
| Databáze: | OpenAIRE |
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