Nitrogen Atom Transfer Catalysis by Metallonitrene C-H Insertion: Photocatalytic Amidation of Aldehydes.

ABSTRACT: C-H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C-H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd-N) with a diradical nitrogen ligand that is singly bonded to Pd^II . Despite the subvalent nitrene character, selective C-H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N₃ SiMe

SUBMITTER: Schmidt-Rantsch T 

PROVIDER: S-EPMC9305406 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature