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.
Cu(II)-promoted oxidative C-N bond cleavage of N-benzoylamino acids to primary aryl amides
Zhou, Liandi,Liu, Wei,Zhao, Yongli,Chen, Junmin
, p. 52 - 62 (2021/02/06)
A novel protocol for CuCl2-promoted oxidative C-N bond cleavage of N-benzoyl amino acids was developed. It is the first example of using accessible amino acid as an ammonia synthetic equivalent for the synthesis of primary aryl amides via CuCl2-promoted oxidative C-N bond cleavage reaction. The present protocol shows excellent functional group tolerance and provides an alternative method for the synthetic of primary aryl amides in 84-96% yields.
Amide bond formation in aqueous solution: Direct coupling of metal carboxylate salts with ammonium salts at room temperature
Nielsen, John,Tung, Truong Thanh
supporting information, p. 10073 - 10080 (2021/12/10)
Herein, we report a green, expeditious, and practically simple protocol for direct coupling of carboxylate salts and ammonium salts under ACN/H2O conditions at room temperature without the addition of tertiary amine bases. The water-soluble coupling reagent EDC·HCl is a key component in the reaction. The reaction runs smoothly with unsubstituted/substituted ammonium salts and provides a clean product without column chromatography. Our reaction tolerates both carboxylate (which are unstable in other forms) and amine salts (which are unstable/volatile when present in free form). We believe that the reported method could be used as an alternative and suitable method at the laboratory and industrial scales. This journal is