40938-35-0Relevant academic research and scientific papers
Room-temperature copper-catalyzed electrophilic amination of arylcadmium iodides with ketoximes
Korkmaz, Adem
, p. 3119 - 3125 (2021/05/10)
We started our study by preparation two ketoximes. Later, there were studies to reveal these ketoximes' effects in the electrophilic amination reaction with organocadmium reagents. Primarily, it was observed that arylcadmium iodides could not be reacted with ketoximes at room temperature in the absence of a catalyst. CuCN was a suitable catalyst for this electrophilic amination reaction of arylcadmium iodides and allowed the preparation of functionalized aniline derivatives in good yields under mild reaction conditions. We obtained the results indicated that the yield of primary arylamines was strongly dependent on the steric and electronic effects of organocadmium reagent and amination agent. In the case of both amination reagents, meta-substituted arylamines were obtained in higher yields than para-substituted arylamines. We observed that acetone O-(4-chlorophenylsulfonyl)oxime, 1, as an aminating agent, was more successful than acetone O-(2-Naphthylsulfonyl)oxime, 2, in the synthesis of functionalized arylamines by electrophilic amination of corresponding aryl cadmium iodides. In this method, there is no cadmium release to the environment.
Aryl C-N bond formation by electrophilic amination of diarylcadmium reagents with O-substituted ketoximes
Da?kapan, Tahir,Korkmaz, Adem
, p. 813 - 817 (2016/07/06)
Diorganocadmium reagents cannot react with ketoxime at room temperature. CuCN catalysis allows diarylcadmium reagents to react with ketoxime and to give corresponding arylamines in good to high yields at room temperature. According to the electronic effects of the substituent attached to the aromatic ring, functionalized diarylcadmium reagents show meta-para selectivity in their amination reactions. Also compared to diarylzinc reagents, diarylcadmium reagents react with O-substituted ketoxime under milder reaction conditions and they form corresponding arylamines in higher yields. CuCN cannot help dialkyl-, dicycloalky-, and dibenzylcadmium reagents to react with ketoxime. Our Aryl C-N bond formation method does not include cadmium excretion into the environment.
Scope and mechanistic study of the ruthenium-catalyzed ortho-C-H bond activation and cyclization reactions of arylamines with terminal alkynes
Yi, Chae S.,Yun, Sang Young
, p. 17000 - 17006 (2007/10/03)
The cationic ruthenium hydride complex [(PCy3) 2(CO)(CH3CN)2RuH]+BF 4- was found to be a highly effective catalyst for the C-H bond activation reaction of arylamines and terminal alkynes. The regioselective catalytic synthesis of substituted quinoline and quinoxaline derivatives was achieved from the ortho-C-H bond activation reaction of arylamines and terminal alkynes by using the catalyst Ru3-(CO)12/HBF 4·OEt2. The normal isotope effect (k CH/kCD = 2.5) was observed for the reaction of C 6H5NH2 and C6D5NH 2 with propyne. A highly negative Hammett value (ρ = -4.4) was obtained from the correlation of the relative rates from a series of meta-substituted anilines, m-XC6H4NH2, with σp in the presence of Ru3(CO)12/ HBF4·OEt2 (3 mol % Ru, 1:3 molar ratio). The deuterium labeling studies from the reactions of both indoline and acyclic arylamines with DC≡CPh showed that the alkyne C-H bond activation step is reversible. The crossover experiment from the reaction of 1-(2-amino-1-phenyl)pyrrole with DC≡CPh and HC≡CC6H4-p-OMe led to preferential deuterium incorporation to the phenyl-substituted quinoline product. A mechanism involving rate-determining ortho-C-H bond activation and intramolecular C-N bond formation steps via an unsaturated cationic ruthenium acetylide complex has been proposed.
