2866-82-2Relevant articles and documents
Approach toward the understanding of coupling mechanism for EDC reagent in solvent-free mechanosynthesis
Wróblewska, Aneta,Paluch, Piotr,Wielgus, Ewelina,Bujacz, Grzegorz,Dudek, Marta K.,Potrzebowski, Marek J.
, p. 5360 - 5363 (2017)
A unique approach in mechanosynthesis, joining solid-state NMR spectroscopy, X-ray crystallography, and theoretical calculations, is employed for the first time to study the mechanism of the formation of the C- N amide bond using EDC?HCl as a coupling reagent. It has been proved that EDC?HCl, which in the crystal lattice exists exclusively in the cyclic form (X-ray data), easily undergoes transformation to a pseudocyclic stable intermediate in reaction with carboxylic acid forming a low-melt phase (differential scanning calorimetry, solid-state NMR). The obtained intermediate is reactive and can be further used for synthesis of amides in reaction with appropriate amines.
In Situ Formation of Cationic π-Allylpalladium Precatalysts in Alcoholic Solvents: Application to C-N Bond Formation
Steinsoultz, Philippe,Bailly, Aurélien,Wagner, Patrick,Oliva, Estefania,Schmitt, Martine,Grimaud, Laurence,Bihel, Frédéric
, p. 560 - 567 (2022/01/03)
We report an efficient Buchwald-Hartwig cross-coupling reaction in alcoholic solvent, in which a low catalyst loading showed excellent performance for coupling aryl halides (I, Br, and Cl) with a broad set of amines, amides, ureas, and carbamates under mild conditions. Mechanistically speaking, in a protic and polar medium, extremely bulky biarylphosphine ligands interact with the dimeric precatalyst [Pd(π-(R)-allyl)Cl]2 to form the corresponding cationic complexes [Pd(π-(R)-allyl)(L)]Cl in situ and spontaneously. The resulting precatalyst further evolves under basic conditions into the corresponding L-Pd(0) catalyst, which is commonly employed for cross-coupling reactions. This mechanistic study highlights the prominent role of alcoholic solvents for the formation of the active catalyst.
Practical one-pot amidation of N -Alloc-, N -Boc-, and N -Cbz protected amines under mild conditions
Hong, Wan Pyo,Tran, Van Hieu,Kim, Hee-Kwon
, p. 15890 - 15895 (2021/05/19)
A facile one-pot synthesis of amides from N-Alloc-, N-Boc-, and N-Cbz-protected amines has been described. The reactions involve the use of isocyanate intermediates, which are generated in situ in the presence of 2-chloropyridine and trifluoromethanesulfonyl anhydride, to react with Grignard reagents to produce the corresponding amides. Using this reaction protocol, a variety of N-Alloc-, N-Boc-, and N-Cbz-protected aliphatic amines and aryl amines were efficiently converted to amides with high yields. This method is highly effective for the synthesis of amides and offers a promising approach for facile amidation.
Fe-mediated synthesis of: N -aryl amides from nitroarenes and acyl chlorides
Wu, Yundong,Guo, Lei,Liu, Yuxuan,Xiang, Jiannan,Jiang, Jun
, p. 15290 - 15295 (2021/05/19)
Amides are prevalent in nature and valuable functional compounds in agrochemical, pharmaceutical, and materials industries. In this work, we developed a selective and mild method for the synthesis of N-aryl amides. Starting from commercially available nitroarenes and acyl halides, N-aryl amides with good yields can be obtained in water. Especially in the process of transformation, Fe dust is the only reductant and additive, and the reaction can be easily performed on a large scale.
