33322-65-5

Upstream product

• 18503-89-4 N,N-dimethylformamide diisopropyl acetal 
• 134-85-0 4-chlorobenzophenone 
• 90-90-4 (4-bromophenyl)(phenyl)methanone 
• 18469-37-9 4-bromo-N,N-dimethylbenzamide 
• 100-52-7 benzaldehyde 
• 83575-59-1 (4-Benzoyl-phenyl)-trimethylsilanyloxy-acetonitrile 
• 20912-50-9 4-benzoylbenzaldehyde 
• 83575-87-5 (4-Benzoyl-phenyl)-dimethylamino-trimethylsilanyloxy-acetonitrile 
• 39148-58-8 4-benzoylbenzoyl chloride 
• 124-40-3 dimethyl amine 

Relevant academic research and scientific papers

Palladium-Catalyzed Aminocarbonylation of Aryl Halides with N,N-Dialkylformamide Acetals

We developed a protocol for the palladium-catalyzed aminocarbonylation of aryl halides using less-toxic formamide acetals as bench-stable aminocarbonyl sources under neutral conditions. Various aryl (including heteroaryl) halides reacted with N,N-dialkylformamide acetals in the presence of a catalytic amount of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct and xantphos to give the corresponding aromatic carboxamides at 90–140 °C without any activating agents or bases in up to quantitative chemical yield. This protocol was applied to aryl bromides, aryl iodides, and trifluoromethanesulfonic acid, as well as to relatively less-reactive aryl chlorides. A wide range of functionalities on the aromatic ring of the substrates were tolerated under the aminocarbonylation conditions. The catalytic aminocarbonylation was used to prepare the insect repellent N,N-diethyl-3-methylbenzamide as well as a synthetic intermediate of the dihydrofolate reductase inhibitor triazinate.

Palladium-catalyzed synthesis of diaryl ketones from aldehydes and (hetero)aryl halides via C-H bond activation

We developed a palladium-catalyzed C-H transformation that enabled the synthesis of ketones from aldehydes and (hetero)aryl halides. The use of picolinamide ligands was key to achieving the transformation. Heteroaryl ketones, as well as diaryl ketones, were synthesized in good to excellent yields, even in gram-scale, using this reaction. Results of density functional theory (DFT) calculations support the C-H bond activation pathway.

ELECTROPHILIC AMINATION OF ACYL ANION EQUIVALENTS: MILD OXIDATION OF ALDEHYDES TO AMIDES VIA O-(TRIMETHYLSILYL)ALDEHYDE CYANOHYDRIN ANIONS

The O-(trimethylsilyl)aldehyde cyanohydrin anions 4a-p(1-)*Li(1+) react with 5 to the amines 6.This electrophilic amination corresponds to a mild and specific oxidation of the aldehydes 1a-p to the amides 7a-p.