A Chiral Bis(arsine) Ligand: synthesis and applications in Palladium catalyzed asymmetric Allylic Alkylations

The new chiral bis(arsine) ligand N,N′-bis[2′- (diphenylarsino)benzoyl]-(1R,2R)-cyclohexanediamine (BiAsBA, 3), based on the backbone of the Trost modular ligand (TML), was synthesized in three steps. A useful approach to introduce the −AsPh2 group on arsine ligands by Pd-catalyzed arsination was us...

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Detalhes bibliográficos
Autores: Uberman, Paula Marina, Caira, Mino R., Martín, Sandra Elizabeth
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2013
País:Argentina
Recursos:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/25413
Acesso em linha:http://hdl.handle.net/11336/25413
Access Level:acceso abierto
Palavra-chave:Arsine Chiral Ligand
Asymmetric Allylic Alkylation
Palladium
Catalyzed Arsination
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descrição
Resumo:The new chiral bis(arsine) ligand N,N′-bis[2′- (diphenylarsino)benzoyl]-(1R,2R)-cyclohexanediamine (BiAsBA, 3), based on the backbone of the Trost modular ligand (TML), was synthesized in three steps. A useful approach to introduce the −AsPh2 group on arsine ligands by Pd-catalyzed arsination was used. The molecular structure and configuration of the BiAsBA ligand was determined by single-crystal X-ray crystallography. In the asymmetric allylic alkylation of 1,3-diphenyl-2- propenyl acetate with dimethyl malonate very high to complete conversion and modest enantioselectivity were achieved. Despite the low enantioselectivity obtained, the bis(arsine) ligand BiAsBA showed significant potential, since it provided a higher ee value than the phosphorus-containing homologous “Trost standard ligand” (TSL) with the same substrate.