101927-54-2Relevant articles and documents
The scope and limitation of nickel-catalyzed aminocarbonylation of aryl bromides from formamide derivatives
Jo, Youngshin,Ju, Jinhun,Choe, Jaehoon,Kwang, Ho Song,Lee, Sunwoo
, p. 6358 - 6361 (2009)
(Chemical Equation Presented) Nickel-catalyzed aminocarbonylation of aryl halides is described. A well-defined air-stable nickel-phosphite catalytic system (Ni(OAc)2 · 4H2O/phosphite 1) effectively promoted the aminocarbonylation of
A convenient one-pot synthesis of: N -substituted amidoximes and their application toward 1,2,4-oxadiazol-5-ones
Phakhodee, Wong,Duangkamol, Chuthamat,Wiriya, Nitaya,Pattarawarapan, Mookda
, p. 38281 - 38288 (2018/12/02)
The first direct one-pot approach for the synthesis of N-substituted amidoximes from secondary amides or the intermediate amides has been developed. Through the Ph3P-I2-mediated dehydrative condensation, a variety of N-aryl and N-alkyl amidoximes (R1(CNOH)NHR2, where R1 or R2 = aryl, alkyl, or benzyl) were readily afforded under mild conditions and short reaction times. The synthetic application of the obtained amidoximes has also been demonstrated through the formation of 1,2,4-oxadiazolones via base-mediated carbonylative cyclization with 1,1′-carbonyldiimidazole.
Integration of co2 reduction with subsequent carbonylation: Towards extending chemical utilization of co2
Lang, Xian-Dong,He, Liang-Nian
, p. , 2062 (2018/10/20)
Currently, it still remains a challenge to amplify the spectrum of chemical fixation of CO2, although enormous progress has been achieved in this field. In view of the widespread applications of CO in a myriad of industrial carbonylation processes, an alternative strategy is proposed in which CO2 reduction to CO is combined with carbonylation with CO generated ex situ, which affords efficiently pharmaceutically and agrochemically attractive molecules. As such, CO2 in this study was efficiently reduced by triphenysilane using CsF to CO in a sealed two-chamber reactor. Subsequently, palladium-catalyzed aminocar-bonylation, carbonylative Sonogashira coupling of aryl iodides, and rhodium(I)-mediated Pauson–Khand-type reaction proceeded smoothly to yield amides, alkynones, and bicyclic cy-clopentenones, respectively. Furthermore, the formed alkynones can further be successfully converted to a series of heterocycles, for example, pyrazoles, 3a-hydroxyisoxazolo[3,2-a]isoindol-8-(3aH)-one derivatives and pyrimidines in moderate yields. The striking features of this protocol include operational simplicity, high efficiency, and relatively broad application scope, which represents an alternative avenue for CO2 transformation.
Ruthenium-catalyzed oxidative decyanative cross-coupling of acetonitriles with amines in air: A general access to primary to tertiary amides under mild conditions
Wang, Yuguang,Wu, Zhongli,Li, Qin,Zhu, Bingchun,Yu, Lei
, p. 3747 - 3757 (2017/09/07)
Catalyzed by Ru and in the presence of air and nucleophiles such as amines or ammonia, activation of the C-CN bond could be easily achieved under mild conditions to produce primary to tertiary amides in good to excellent yields. The use of accessible and functional-group-tolerant starting materials, a cheap, low-loading and recyclable catalyst, ligand-free conditions and excellent product yields are the advantages of the method. Moreover, compared with the Ritter reaction and hydration methods, this novel reaction has more comprehensive application scope.
Copper-catalyzed intermolecular amidation and imidation of unactivated alkanes
Tran, Ba L.,Li, Bijie,Driess, Matthias,Hartwig, John F.
supporting information, p. 2555 - 2563 (2014/03/21)
We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C-H bonds over tertiary C-H bonds and even occur at primary C-H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO) 2 at 100 C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C-H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C-H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product.
Radical mediated-direct conversion of aldehydes into acid bromides
Kang, Dong Ho,Joo, Tae Young,Chavasiri, Warinthorn,Jang, Doo Ok
, p. 285 - 287 (2007/10/03)
A method of preparing acid bromides directly from aldehydes with Br3CCO2Et under radical conditions was developed. Aromatic aldehydes with electron-donating group were found to be more reactive than aromatic aldehydes with electron-w
A mild and efficient reaction for conversion of carboxylic acids into acid bromides with ethyl tribromoacetate/triphenylphosphine under acid-free conditions
Kang, Dong Ho,Joo, Tae Young,Lee, Eun Hwa,Chaysripongkul, Skaydaw,Chavasiri, Warinthorn,Jang, Doo Ok
, p. 5693 - 5696 (2007/10/03)
Acid bromides were prepared efficiently from carboxylic acids with readily available ethyl tribromoacetate and triphenylphosphine at room temperature under neutral conditions. The present process is applicable to the preparation of various acid bromides from aromatic and aliphatic carboxylic acids. Aromatic carboxylic acids were found to be more reactive than aliphatic carboxylic acids under reaction conditions.
A mild and efficient procedure for the preparation of acid chlorides from carboxylic acids
Jang, Doo Ok,Park, Doo Jin,Joonggon, Kim
, p. 5323 - 5326 (2007/10/03)
Various carboxylic acids are converted into the corresponding acid chlorides by treatment with trichloroacetonitrile and triphenylphosphine in methylene chloride at room temperature. Aryl acids show higher reactivity than alkyl acids under the conditions.
