Stereogenic-at-iron mesoionic carbene complex for enantioselective C-H amidation.

Electronically tuned C 2 -symmetric stereogenic-at-iron complexes, featuring strongly σ-donating 1,2,3-triazolin-5-ylidene mesoionic carbene (MIC) ligands, exhibit enhanced catalytic efficiency compared to conventional imidazol-2-ylidene analogs, as demonstrated in nitrene-mediated ring-closing C(sp 3 )-H amidation reactions. Furthermore, a chiral pinene-derived pyridyl triazole ligand enables a highly diastereoselective synthesis of a non-racemic chiral iron catalyst, thereby controlling the absolute configuration at the metal center, as confirmed by NMR and X-ray crystallography. This pinene-modified stereogenic-at-iron MIC complex demonstrates high catalytic activity and a respectable asymmetric induction in the ring-closing C(sp 3 )-H amination of N -benzoyloxyurea, yielding 2-imidazolidinones with enantiomeric ratios of up to 92 : 8. These findings reflect the profound potential of this new class of mesoionic carbene iron complexes in further understanding and tuning the reactivity of iron-based catalysts.