Affiliation:
1. Departamento de Catálisis y Procesos Catalíticos Departamento de Química Inorgánica Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) CSIC – Universidad de Zaragoza Pedro Cerbuna 12 50009 Zaragoza Spain
Abstract
AbstractThe unique dynamic configuration of an enantioselective chiral‐at‐metal catalyst based on Rh(III) and a non‐chiral tetradentate ligand is described and resolved. At room temperature, the catalyst undergoes a dynamic configuration process leading to the formation of two interconvertible metal‐stereoisomers, remarkably without racemization. Density functional theory (DFT) calculations indicate that this metal‐isomerization proceeds via a concerted transition state, which features a trigonal bipyramidal geometry stabilized by the tetradentate ligand. Furthermore, the resolved enantiopure complex shows high catalytic enantioinduction in the Friedel‐Crafts reaction, achieving enantiomeric ratios as high as 99 : 1.
Funder
Ministerio de Ciencia e Innovación
Subject
General Chemistry,Catalysis,Organic Chemistry