Synthesis of chiral organotins suitable for the preparation of asymmetric heterogeneous catalysts

A key step in the preparation of asymmetric heterogeneous catalysts based on silica-supported rhodium and platinum chemically modified with chiral organotins, is the synthesis of optically pure tin derivatives. We report on the synthetic pathways leading to the synthesis of (-)-menthyltin derivative...

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Detalles Bibliográficos
Autores: Faraoni, María Belén, Ayala, Alicia D., Vetere, Virginia, Casella, Mónica Laura, Ferretti, Osmar Alberto, Podesté, Julio C.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2005
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/55201
Acceso en línea:http://hdl.handle.net/11336/55201
Access Level:acceso abierto
Palabra clave:Chiral Ligand
Heterogeneous Catalysts
Hydrogenation
Organotin
Synthesis
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descripción
Sumario:A key step in the preparation of asymmetric heterogeneous catalysts based on silica-supported rhodium and platinum chemically modified with chiral organotins, is the synthesis of optically pure tin derivatives. We report on the synthetic pathways leading to the synthesis of (-)-menthyltin derivatives without the formation of epimerization by-products. The physical properties (including full 1H, 13C and 119Sn NMR spectra) of the new compounds, containing between one and three (-)-menthyl ligands attached to the tin atom, are reported. The preparation of two catalysts based on silica-supported rhodium and platinum chemically modified with (-)-menthyldiphenylmethyltin, as well as some studies on the catalytic hydrogenation of ethyl pyruvate, are also described. These studies show that the reductions lead to (R)- and (S)-ethyl lactates as the only products, that the (S) enantiomer was the isomer formed preferentially, and that the degree of conversion observed using both catalytic systems was almost quantitative (97-100%). The enantiomeric excesses observed were in the range 7-8%. One important advantage of these catalytic systems is their stability. Recycling of the used catalysts is possible, without any loss in the degree of conversion or enantiomeric excess.