Catalytic Amination of Aldehydes to Amides

Abstract

Aldehydes react in a disproportionation reaction in the presence of rhodium catalysts to yield amines and amides. By adding N-methylmorpholine N-oxide as an oxidant in the presence of catalytic amounts of rhodium, the oxidative am- [a] 523 ination of aldehydes proceeds selectively to give the corresponding amide. Both aliphatic and aromatic aldehydes react with secondary amines to yield carboxylic acid amides in good to excellent yields.

Heterobimetallic clusters of Na8Ln(OtBu)10(OH) as homogeneous catalysts for amidation of aldehydes with amines

“…The direct amidation of aldehydes with amines is the most desired approach to amides because it is economical and starting materials are readily available. Various efficient catalysts have been explored for this process [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]; however, some of these systems require the use of peroxide [2,3], heating, or equivalent alkali metal amides [5]. Since the first example of amidation of aldehydes with amines catalyzed by homoleptic lanthanide amides was reported [17], various lanthanide complexes, such as tris-guanidinate lanthanide complexes [18], bis-amidinate lanthanide complexes [19] and anionic lanthanide aryloxides [20], have been shown to behave as efficient catalysts under mild conditions.…”

“…The desired addition sequence for the reaction requires that amine is added to the catalyst solution first, followed by the aldehyde after 30 min. Higher yields were achieved when the reaction was performed in THF rather than under solvent-free conditions (Table 1, entries 3,9). Increasing the reaction time did not improve the yield (Table 1, entries 3,11).…”

Iron‐Catalyzed Amidation of Aldehydes with N‐Chloroamines

“…Several examples of aldehyde amidation via oxidation of intermediate carbinolamines have been recently reported. Usually these reactions are catalyzed by transition metals, such as Cu,4 Rh,5 Ru,6 Pd,7 Ni,8 and Fe,9 but metal‐free oxidative procedures have also been reported 10. The Cannizzaro reaction affords another practical route toward the one‐pot transformation of aldehydes into amides 11.…”

Recent developments in oxidative esterification and amidation of aldehydes

“…Generally these procedures were catalysed by metals, such as Rh, 20 Ru, 21 Pd, 22 Ni. 23 However the major drawback is due to the formation and stability of the hemiaminal intermediate, and is closely related to the steric attributes of the aldehyde and the amine.…”