40095-13-4

Upstream product

• 21048-30-6 benzoic acid-O₁₈ 
• 100-47-0 benzonitrile 
• 932-90-1 syn-benzaldehyde oxime 
• 100-46-9 benzylamine 
• 55-21-0 benzamide 

Relevant academic research and scientific papers

Highly Selective Ruthenium-Catalyzed Direct Oxygenation of Amines to Amides

Reports on aerobic oxidation of amines to amides are rare, and those reported suffer from several limitations like poor yield or selectivity and make use of pure oxygen under elevated pressure. Herein, we report a practical and an efficient ruthenium-catalyzed synthetic protocol that enables selective oxidation of a broad range of primary aliphatic, heterocyclic and benzylic amines to their corresponding amides, using readily available reagents and ambient air as the sole oxidant. Secondary amines instead, yield benzamides selectively as the sole product. Mechanistic investigations reveal intermediacy of nitriles, which undergo hydration to afford amide as the final product.

Atom-Economical and Tandem Conversion of Nitriles to N-Methylated Amides Using Methanol and Water

A cobalt complex catalyzed tandem conversion of nitrile to N-methylated amide is described using a methanol and water mixture. Using this protocol, several nitriles were directly and efficiently converted to the desired N-methylated amides. Kinetic experiments using H2O18 and CD3OD suggested that water and methanol were the source of the oxygen atom and methyl group, respectively, in the final N-methylated amides. Importantly, the participation of active Co(I)-H species in this transformation was realized from the control experiment. The kinetic isotope effect (KIE) study suggested that the activation of the C-H bond of methanol was a kinetically important step. The Hammett plot confirmed that the reaction was faster with the electron deficient nitriles. In addition, the plausible pathway for the formation of N-methylated amides from the nitriles was supported by the computational study.

Ruthenium-catalyzed rearrangement of aldoximes to primary amides in water

The rearrangement of aldoximes to primary amides has been studied using the readily available arene-ruthenium(II) complex [RuCl2(η 6-C6Me6){P(NMe2)3}] (5 mol %) as catalyst. Reactions proceeded cleanly in pure water at 100 °C without the assistance of any cocatalyst, affording the desired amides in high yields (70-90%) after short reaction times (1-7 h). The process was operative with both aromatic, heteroaromatic, α,β-unsaturated, and aliphatic aldoximes and tolerated several functional groups. Reaction profiles and experiments using 18O-labeled water indicate that two different mechanisms are implicated in these transformations. In both of them, nitrile intermediates are initially formed by dehydration of the aldoximes. These intermediates are then hydrated to the corresponding amides by the action of a second molecule of aldoxime or water. A kinetic analysis of the rearrangement of benzaldoxime to benzamide is also discussed.

Heterogeneously catalyzed efficient oxygenation of primary amines to amides by a supported ruthenium hydroxide catalyst

(Chemical Equation Presented) Supporting green chemistry: The supported ruthenium hydroxide Ru(OH)x/Al2O3 acts as an efficient heterogeneous catalyst for the oxygenation of primary amines to primary amides (see scheme). Various primary amines (including aromatic, aliphatic, and heterocyclic) are converted in aqueous media, using air as the sole oxidant and producing only water as a by-product.

C2-amidoglycosylation. Scope and mechanism of nitrogen transfer

A one-pot C2-amidoglycosylation reaction for the synthesis of 2-N-acyl-2-deoxy-β-pyranosides from glycals is described. Glycal donors activated by the reagent combination of thianthrene-5-oxide (11) and Tf2O, followed by treatment with an amide nucleophile and a glycosyl acceptor, lead to the formation of various C2-amidoglycoconjugates. Both the C2-nitrogen transfer and the glycosidic bond formation proceed stereoselectively, allowing for the introduction of both natural and nonnatural amide functionalities at C2 with concomitant anomeric bond formation in a one-pot procedure. Tracking of the reaction by low-temperature NMR spectroscopy employing 15N- and 18O-isotope labels suggests a mechanism involving the formation of the C2-sulfonium glycosyl imidate 39 as well as oxazoline 37 as key intermediates in this novel oxidative glycosylation process.