824-75-9Relevant articles and documents
Nitrogen Atom Transfer Catalysis by Metallonitrene C?H Insertion: Photocatalytic Amidation of Aldehydes
Schmidt-R?ntsch, 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
, (2022/01/20)
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.
Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation
Ben-David, Yehoshoa,Diskin-Posner, Yael,Kar, Sayan,Milstein, David,Zhou, Quan-Quan,Zou, You-Quan
, p. 10239 - 10245 (2021/08/24)
A simple and efficient system for the hydration and α-deuteration of nitriles to form amides, α-deuterated nitriles, and α-deuterated amides catalyzed by a single pincer complex of the earth-abundant manganese capable of metal-ligand cooperation is reported. The reaction is selective and tolerates a wide range of functional groups, giving the corresponding amides in moderate to good yields. Changing the solvent from tert-butanol to toluene and using D2O results in formation of α-deuterated nitriles in high selectivity. Moreover, α-deuterated amides can be obtained in one step directly from nitriles and D2O in THF. Preliminary mechanistic studies suggest the transformations contributing toward activation of the nitriles via a metal-ligand cooperative pathway, generating the manganese ketimido and enamido pincer complexes as the key intermediates for further transformations.
Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
An, Duk Keun,Jaladi, Ashok Kumar,Kim, Hyun Tae,Yi, Jaeeun
supporting information, (2021/11/17)
Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
