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

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Defense Thèse de doctorat : Univ. Genève, 2012 - Sc. 4503 - 2012/10/26
Abstract 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.
Keywords CatalysisPalladiumOxindoleIndoline
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URN: urn:nbn:ch:unige-255591
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KATAYEV, Dmitry. Chiral N-heterocyclic carbene (NHC) ligands in Pd-catalyzed cross-coupling reactions. Université de Genève. Thèse, 2012. https://archive-ouverte.unige.ch/unige:25559

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Deposited on : 2013-01-16

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