Nitrogen Atom Transfer Catalysis by Metallonitrene CH Insertion: Photocatalytic Amidation of Aldehydes Academic Article uri icon

abstract

  • AbstractCH amination and amidation by catalytic nitrene transfer are wellestablished and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into CH 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 (PdN) with a diradical nitrogen ligand that is singly bonded to PdII. Despite the subvalent nitrene character, selective CH insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3SiMe3. Based on these results, a photocatalytic protocol for aldehyde CH trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic CH nitrogen atom transfer offers facile access to primary amides after deprotection.

published proceedings

  • Angewandte Chemie

altmetric score

  • 7.85

author list (cited authors)

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

citation count

  • 0

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

  • February 2022

publisher