Nitrogen Atom Transfer Catalysis by Metallonitrene C–H Insertion: Photocatalytic Amidation of Aldehydes
2022-01-14 | journal article. A publication with affiliation to the University of Göttingen.
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Nitrogen Atom Transfer Catalysis by Metallonitrene C–H Insertion: Photocatalytic Amidation of Aldehydes
Schmidt-Räntsch, T.; Verplancke, H.; Lienert, J. N.; Otte, M.; Van Trieste, G. P.; Reid, K. A. & Reibenspies, J. H. et al. (2022)
Angewandte Chemie International Edition, 61(9). DOI: https://doi.org/10.1002/anie.202115626
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Details
- Authors
- Schmidt-Räntsch, Till; Verplancke, Hendrik; Lienert, Jonas N.; Otte, Matthias; Van Trieste, Gerard P.; Reid, Kaleb A.; Reibenspies, Joseph H.; Powers, David C.; Holthausen, Max C.; Schneider, Sven; Demeshko, Serhiy
- 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 N3SiMe3. 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.
- Issue Date
- 14-January-2022
- Journal
- Angewandte Chemie International Edition
- ISSN
- 1433-7851
- eISSN
- 1521-3773
- Language
- English
- Sponsor
- European Research Council http://dx.doi.org/10.13039/100010663
Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659
U.S. Department of Energy http://dx.doi.org/10.13039/100000015
Welch Foundation http://dx.doi.org/10.13039/100000928
National Science Foundation http://dx.doi.org/10.13039/100000001