Doctoral thesis
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Chiral N-heterocyclic carbene (NHC) ligands in Pd-catalyzed cross-coupling reactions

ContributorsKatayev, Dmitry
Defense date2012-10-26

New chiral N-heterocyclic carbene (NHC) ligands have been developed and applied in the asymmetric Pd-catalyzed intramolecular a-arylation of amides producing 3,3-disubstituted-, spiro-, and aza-spirooxindoles in high yields (up to 99%) and excellent enantioselectivities (up to 97% ee). For the first time a palladacycle intermediates were isolated and fully characterized including X-ray crystal structure determinations. Analysis of these solid state structures demonstrates the importance of both the bulky tert-butyl groups and ortho-substituted aryl rings at the stereogenic centers of the ligand. Additionally, an extraordinarily efficient palladium-NHC catalyzed synthesis of highly enantioenriched 2,3-trans-fused indolines via asymmetric C(sp3)-H activation of an unactivated methylene unit was developed. It is noteworthy that this C-C coupling delivers the products with enantioselectivities of up to 95% ee despite the high temperature required. The initial results were extended to the synthesis of 2- and 2,3-disubstituted indolines. Racemic substrates reacted via highly asymmetric regiodivergent reactions.

  • Catalysis
  • Palladium
  • Oxindole
  • Indoline
Citation (ISO format)
KATAYEV, Dmitry. Chiral N-heterocyclic carbene (NHC) ligands in Pd-catalyzed cross-coupling reactions. 2012. doi: 10.13097/archive-ouverte/unige:25559
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Creation01/14/2013 11:24:00 AM
First validation01/14/2013 11:24:00 AM
Update time03/14/2023 7:57:27 PM
Status update03/14/2023 7:57:26 PM
Last indexation10/18/2023 3:26:37 PM
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