Rhodium-Catalyzed Pauson−Khand Reaction Using a Small-Bite-Angle P‑Stereogenic C1‑Diphosphine Ligand

The asymmetric Pauson−Khand reaction catalyzed by [Rh(COD)(MaxPHOS)]BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the Pstereogenic C1-symmetry small-bite-ang...

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Detalhes bibliográficos
Autores: Cristóbal Lecina, Edgar, Costantino, Andrea R., Grabulosa, Arnald, Riera i Escalé, Antoni, Verdaguer i Espaulella, Xavier
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2015
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/69303
Acesso em linha:https://hdl.handle.net/2445/69303
Access Level:acceso abierto
Palavra-chave:Lligands
Catàlisi asimètrica
Rodi
Reacció de Pauson-Khand
Ligands
Enantioselective catalysis
Rhodium
Pauson-Khand reaction
Descrição
Resumo:The asymmetric Pauson−Khand reaction catalyzed by [Rh(COD)(MaxPHOS)]BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the Pstereogenic C1-symmetry small-bite-angle ligand MaxPHOS is a viable ligand in this process. The formation of [2+2+2] cycloaddition compounds has shown to be a competitive process. A mechanism is proposed to account for the observed results. The intermediate rhodium dicarbonyl complex 6 was synthesized, and its solid-state structure was elucidated by X-ray crystallography.