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Transition metal complexes bearing atropisomeric saturated NHC ligands
Author(s) -
Savchuk Mariia,
Bocquin Lucas,
Albalat Muriel,
Jean Marion,
Vanthuyne Nicolas,
Nava Paola,
Humbel Stéphane,
Hérault Damien,
Clavier Hervé
Publication year - 2022
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.23378
Subject(s) - chemistry , carbene , palladium , transition metal , chirality (physics) , intramolecular force , atropisomer , axial chirality , enantiomer , rhodium , aryl , ligand (biochemistry) , metal , polymer chemistry , stereochemistry , medicinal chemistry , organic chemistry , catalysis , enantioselective synthesis , receptor , biochemistry , chiral symmetry breaking , physics , alkyl , quantum mechanics , nambu–jona lasinio model , quark
From achiral imidazolinium salts, chiral transition metal complexes containing an N‐heterocyclic carbene (NHC) ligand were prepared (metal = palladium, copper, silver, gold, rhodium). Axial chirality in these complexes results from the formation of the metal‐carbene bond leading to the restriction of rotation of dissymmetric N ‐aryl substituents about the C–N bond. When these complexes exhibited a sufficient configurational stability, a resolution by chiral high‐performance liquid chromatography (HPLC) on preparative scale enabled isolation of enantiomers with excellent enantiopurities (>99% ee) and good yields. A study of the enantiomerization barriers revealed the effect of the backbone nature as well as the type of transition metal on its values. Nevertheless, the evaluation of palladium‐based complexes in asymmetric intramolecular α‐arylation of amides demonstrated that the ability to induce an enantioselectivity cannot be correlated to the configurational stability of the precatalysts.