Dynamic Kinetic Resolution of Heterobiaryl Ketones by Zinc-Catalyzed Asymmetric Hydrosilylation
Corresponding Author
Dr. Valentín Hornillos
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092 Sevilla, Spain
Search for more papers by this authorJosé A. Carmona
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092 Sevilla, Spain
Search for more papers by this authorDr. Abel Ros
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092 Sevilla, Spain
Departamento de Química Orgánica (Universidad de Sevilla), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Prof. García González 1, 41012 Sevilla, Spain
Search for more papers by this authorDr. Javier Iglesias-Sigüenza
Departamento de Química Orgánica (Universidad de Sevilla), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Prof. García González 1, 41012 Sevilla, Spain
Search for more papers by this authorDr. Joaquín López-Serrano
Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA)., Universidad de Sevilla and Instituto de Investigaciones Científicas (CSIC-US), Avda. Américo Vespucio 49, 41092 Sevilla, Spain
Search for more papers by this authorCorresponding Author
Prof. Rosario Fernández
Departamento de Química Orgánica (Universidad de Sevilla), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Prof. García González 1, 41012 Sevilla, Spain
Search for more papers by this authorCorresponding Author
Prof. José M. Lassaletta
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092 Sevilla, Spain
Search for more papers by this authorCorresponding Author
Dr. Valentín Hornillos
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092 Sevilla, Spain
Search for more papers by this authorJosé A. Carmona
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092 Sevilla, Spain
Search for more papers by this authorDr. Abel Ros
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092 Sevilla, Spain
Departamento de Química Orgánica (Universidad de Sevilla), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Prof. García González 1, 41012 Sevilla, Spain
Search for more papers by this authorDr. Javier Iglesias-Sigüenza
Departamento de Química Orgánica (Universidad de Sevilla), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Prof. García González 1, 41012 Sevilla, Spain
Search for more papers by this authorDr. Joaquín López-Serrano
Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA)., Universidad de Sevilla and Instituto de Investigaciones Científicas (CSIC-US), Avda. Américo Vespucio 49, 41092 Sevilla, Spain
Search for more papers by this authorCorresponding Author
Prof. Rosario Fernández
Departamento de Química Orgánica (Universidad de Sevilla), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Prof. García González 1, 41012 Sevilla, Spain
Search for more papers by this authorCorresponding Author
Prof. José M. Lassaletta
Instituto Investigaciones Químicas (CSIC-US), Centro de Innovación en Química Avanzada (ORFEO-CINQA), C/ Américo Vespucio 49, 41092 Sevilla, Spain
Search for more papers by this authorDedicated to Professor A. Ulises Acuña
Graphical Abstract
The dynamic duo: A nitrogen atom and the carbonyl group in heterobiaryl ketones form a Lewis pair which is responsible for the labilization of the stereogenic axis, and constitutes the key strategy for developing a zinc-catalyzed asymmetric hydrosilylation by dynamic kinetic resolution. This process simultaneously installs a stereogenic axis and a stereocenter for the highly enantioselective synthesis of heterobiaryl carbinols.
Abstract
A diastereo- and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile heterobiaryl ketones is described. The DKR proceeds by zinc-catalyzed hydrosilylation of the carbonyl group, thus leading to secondary alcohols bearing axial and central chirality. The strategy relies on the labilization of the stereogenic axis that takes place thanks to a Lewis acid–base interaction between a nitrogen atom in the heterocycle and the ketone carbonyl group. The synthetic utility of the methodology is demonstrated through stereospecific transformations into either N,N-ligands or appealing axially chiral, bifunctional thiourea organocatalysts.
Supporting Information
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