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Formation of Quaternary Stereogenic Centers by Copper-Catalyzed Asymmetric Conjugate Addition Reactions of Alkenylaluminums to Trisubstituted Enones |
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Published in | Chemistry. 2013, vol. 19, no. 45, p. 15226-15239 | |
Abstract | Alkenylaluminums undergo asymmetric copper-catalyzed conjugate addition (ACA) to β-substituted enones allowing the formation of stereogenic all-carbon quaternary centers. Phosphinamine–copper complexes proved to be particularly active and selective compared with phosphoramidite ligands. After extensive optimization, high enantioselectivities (up to 96 % ee) were obtained for the addition of alkenylalanes to β-substituted enones. Two strategies for the generation of the requisite alkenylaluminums were explored allowing for the introduction of aryl- and alkyl-substituted alkenyl nucleophiles. Moreover, alkyl-substituted phosphinamine (SimplePhos) ligands were identified for the first time as highly efficient ligands for the Cu-catalyzed ACA. | |
Keywords | Aluminum — Asymmetric synthesis — Conjugate addition — Copper — Phosphorous | |
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Citation (ISO format) | MUELLER, Daniel, ALEXAKIS, Alexandre. Formation of Quaternary Stereogenic Centers by Copper-Catalyzed Asymmetric Conjugate Addition Reactions of Alkenylaluminums to Trisubstituted Enones. In: Chemistry, 2013, vol. 19, n° 45, p. 15226-15239. doi: 10.1002/chem.201302856 https://archive-ouverte.unige.ch/unige:30742 |