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

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 PdII . 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 SiMe3 . Based on these results, a photocatalytic protocol for aldehyde C-H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C-H nitrogen atom transfer offers facile access to primary amides after deprotection.

published proceedings

  • Angew Chem Int Ed Engl

altmetric score

  • 7

author list (cited authors)

  • Schmidt-Rntsch, T., Verplancke, H., Lienert, J. N., Demeshko, S., Otte, M., Van Trieste, G. P., ... Schneider, S.

citation count

  • 3

complete list of authors

  • Schmidt-Räntsch, Till||Verplancke, Hendrik||Lienert, Jonas N||Demeshko, Serhiy||Otte, Matthias||Van Trieste, Gerard P||Reid, Kaleb A||Reibenspies, Joseph H||Powers, David C||Holthausen, Max C||Schneider, Sven

publication date

  • January 1, 2022 11:11 AM

publisher