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- Title
Dynamic Configuration on a Chiral‐at‐Rhodium Catalyst Featuring a Flexible Tetradentate Ligand.
- Authors
Tejero, Alvaro G.; Castillo, Javier; Viguri, Fernando; Carmona, Daniel; Passarelli, Vincenzo; Lahoz, Fernando J.; García‐Orduña, Pilar; Rodríguez, Ricardo
- Abstract
The 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.
- Subjects
CATALYSTS; FRIEDEL-Crafts reaction; DENSITY functional theory; RACEMIZATION; TRANSITION state theory (Chemistry); BASE catalysts
- Publication
Chemistry - A European Journal, 2024, Vol 30, Issue 10, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202303935