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Scientific article
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Formation of Quaternary Stereogenic Centers by Copper-Catalyzed Asymmetric Conjugate Addition Reactions of Alkenylaluminums to Trisubstituted Enones

Published inChemistry, vol. 19, no. 45, p. 15226-15239
Publication date2013
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
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
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ISSN of the journal0947-6539
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