15235-32-2Relevant academic research and scientific papers
Palladium-Catalyzed Aminocarbonylation of Aryl Halides with N,N-Dialkylformamide Acetals
Hirata, Shuichi,Osako, Takao,Uozumi, Yasuhiro
, (2021/10/05)
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.
Aminocarbonylation (hydrazinocarbonylation) of iodoalkenes and iodoarenes
Gergely, Máté,Kollár, László
, p. 838 - 844 (2017/02/05)
Iodoalkenes such as 1-iodocyclohexene, 4-tert-butyl-1-iodocyclohexene, α-iodostyrene and 17-iodoandrost-16-ene were aminocarbonylated in palladium-catalysed reaction using 1,1-disubstituted (cyclic) hydrazines (3-amino-3-azabicyclo[3.3.0]octane and (S)-1-amino-2-methoxymethylpyrrolidine (SAMP)/(R)-1-amino-2-methoxymethyl-pyrrolidine (RAMP)) as N-nucleophiles. The corresponding hydrazides were formed in moderate to high yields. The hydrazinocarbonylation of iodobenzene using the above 1,1-disubstituted hydrazines resulted in a rather complex reaction mixture due to two major types of side-reactions: i) the deamination of the 3-amino-3-azabicyclo[3.3.0]octane, and ii) the double carbon monoxide insertion. In this way, in addition to the expected benzoylhydrazide derivative, phenylglyoxylhydrazide (double CO insertion product) and benzamide (‘deamination’ product) were also formed. By the appropriate modification of the reaction conditions, good selectivities towards the target compounds were achieved even in these cases. The formation of the products/side-products were rationalized on the basis of a simplified catalytic cycle.
An effective synthesis of N,N-dimethylamides from carboxylic acids and a new route from N,N-dimethylamides to 1,2-diaryl-1,2-diketones
Kumagai, Takashi,Anki, Tomohiro,Ebi, Takahiro,Konishi, Akihito,Matsumoto, Kouzou,Kurata, Hiroyuki,Kubo, Takashi,Katsumoto, Kenta,Kitamura, Chitoshi,Kawase, Takeshi
experimental part, p. 8968 - 8973 (2011/01/04)
Carboxylic acids were heated at 150 °C in DMF in the presence of 1.25 equiv of thionyl chloride to give corresponding N,N-dimethylamides in good yields. Tandem chlorination and amidation reactions occurred in the one-pot procedure. Dicarboxylic acids needed prolonged reaction time to produce bisamides in good yields. Some benzamides were efficiently converted into corresponding 1,2-diaryl-1,2-diketones (benzils) under acyloin condensation conditions in the presence of 4,4′-di-tert-butylbiphenyl (DBB) in THF. Ultrasonic irradiation effectively accelerates the reaction, but it is not critical. However, the presence of DBB is fatal to the reaction. Although a few synthetic methods for benzils from benzoic acids have been reported so far, this method is one of the most convenient and highly reproducible procedures.
Aminocarbonylation of aryl halides using a nickel phosphite catalytic system
Ju, Jinhun,Jeong, Miso,Moon, Jeongju,Hyun, Min Jung,Lee, Sunwoo
, p. 4615 - 4618 (2008/03/13)
(Formula Presented) The nickel and phosphite catalytic system with sodium methoxide enables a very efficient aminocarbonylation reaction to be performed between aryl iodides or bromides and N,N-dimethylformamide (DMF). Phosphite ligand 1, which is very st
