P-Stereogenic threonine derived Ir–P,N complexes. Reversiblecyclometallation and asymmetric hydrogenation reactions

A threonine-derived phosphine-oxazoline iridium catalyst is reported, showcasing excellent selectivity in thehydrogenation of N-Boc-2,3-diarylallylamines. The reversible cyclometallation process between the squareplanar Ir(I) complex and the corresponding octahedral Ir(III) species is thoroughly inv...

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Bibliographic Details
Authors: Rojo, Pep, Lledós, Agustí (Lledós i Falcó), Riera i Escalé, Antoni, Verdaguer i Espaulella, Xavier
Format: article
Status:Published version
Publication Date:2023
Country:España
Institution:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repository:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/219786
Online Access:https://hdl.handle.net/2445/219786
Access Level:Open access
Keyword:Lligands
Química analítica
Iridi
Ligands
Analytical chemistry
Iridium
Description
Summary:A threonine-derived phosphine-oxazoline iridium catalyst is reported, showcasing excellent selectivity in thehydrogenation of N-Boc-2,3-diarylallylamines. The reversible cyclometallation process between the squareplanar Ir(I) complex and the corresponding octahedral Ir(III) species is thoroughly investigated, while consideringthe influence of substitution at the phenyl group of the oxazoline on this equilibrium. X-Ray analysis revealsthat the cyclometallated tridentate ligand adopts a fac coordination mode. Furthermore, the catalyticperformance of these complexes in the asymmetric hydrogenation is evaluated and the utilization of Ir(III) precatalystsor Ir(I)/Ir(III) mixtures in hydrogenation reactions is proposed based on the observed equilibriumdynamics.