Artículo
A Dynamic Kinetic C-P Cross-Coupling for the Asymmetric Synthesis of Axially Chiral P,N Ligands
Autor/es | Ramírez-López, Pedro
Ros, Abel Estepa, Beatriz Fernández Fernández, Rosario Fátima Fiser, Béla Gómez-Bengoa, Enrique Lassaletta, José M. |
Departamento | Universidad de Sevilla. Departamento de Química Orgánica |
Fecha de publicación | 2016 |
Fecha de depósito | 2018-06-19 |
Publicado en |
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Resumen | The Pd-catalyzed enantioselective C-P cross-coupling between racemic, configurationally stable heterobiaryl triflates and trialkylsilyldiaryl(dialkyl)phosphines has been used for the synthesis of several families of ... The Pd-catalyzed enantioselective C-P cross-coupling between racemic, configurationally stable heterobiaryl triflates and trialkylsilyldiaryl(dialkyl)phosphines has been used for the synthesis of several families of enantiomerically enriched heterobiaryl phosphines including QUINAP, PINAP, and QUINAZOLINAP analogues, which can be performed with good yields and enantioselectivities using JOSIPHOS-type bidentate phosphines. The strategy relies on two key assumptions: (I) The N atom of the heterocycle is a better ligand than triflate, and upon oxidative addition, it incorporates into the coordination sphere of the Pd center to form cationic cyclic intermediates. (II) The geometry of the palladacycle results in a widening of the angles involved in the stabilization of the stereogenic axis, facilitating a fast interconversion of diastereomeric structures and, hence, a dynamic kinetic C-P cross-coupling reaction. These starting hypotheses are supported by experimental and computational studies. |
Agencias financiadoras | Ministerio de Economía y Competitividad (MINECO). España Junta de Andalucía |
Cita | Ramírez-López, P., Ros, A., Estepa, B., Fernández, R., Fiser, B., Gómez-Bengoa, E. y Lassaletta, J.M. (2016). A Dynamic Kinetic C-P Cross-Coupling for the Asymmetric Synthesis of Axially Chiral P,N Ligands. ACS Catalysis, 6 (6), 3955-3964. |
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