Nitrogen Atom Transfer Catalysis by Metallonitrene C-H Insertion: Photocatalytic Amidation of Aldehydes.
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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.
author list (cited authors)
Schmidt-Rntsch, T., Verplancke, H., Lienert, J. N., Demeshko, S., Otte, M., Van Trieste, G. P., ... Schneider, S.
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