33739-91-2Relevant academic research and scientific papers
Cobalt catalysed aminocarbonylation of thiols in batch and flow for the preparation of amides
Domínguez, Gema,Ordu?a, Jose Maria,Pérez-Castells, Javier
, p. 30398 - 30406 (2021/10/20)
The synthesis of amides from thiols through a cobalt-catalyzed aminocarbonylation is shown. After optimizing all the reaction parameters, the methodology makes possible the obtention of amides with variable yields, while competing reactions such as the formation of disulfides and ureas can be limited. The process works well with aromatic thiols with electron donating groups (EDG) whereas other thiols give reaction with lower yields. The previous process has been transferred and optimized into flow equipment, thus allowing using less CO in a safer way, and permitting the scaling up of the synthesis. Two drugs, moclobemide and itopride were prepared with this methodology, albeit only in the second case with good results. A mechanistic pathway is proposed.
Metal-free Photocatalytic Intermolecular anti-Markovnikov Hydroamination of Unactivated Alkenes
Li, Juncheng,Wang, Ting,Zhao, Gaoyuan
supporting information, p. 2650 - 2654 (2021/06/25)
The development of photocatalytic intermolecular hydroamination reaction between N-aminated dihydropyridines and unactivated alkenes is reported. Metal-free co-catalysts, rhodamine 6G and thiophenol, in presence of visible light are used to initiate the process. The transformation shows a broad substrate scope, both alkenes and amidyl radical can act as coupling partners. The radical strategy provides excellent anti-Markovnikov selectivity and regioselectivity in diene substrates.
A case study of Pd?Pd intramolecular interaction in a benzothiazole based palladacycle; catalytic activity toward amide synthesisviaan isocyanide insertion pathway
Loni, Masood,Balmohammadi, Yaser,Dadgar Yeganeh, Reza,Imani, Kaveh,Notash, Behrouz,Bazgir, Ayoob
supporting information, p. 3290 - 3297 (2021/02/26)
An acetate bridge benzothiazolepalladacycle containing a rare metallophilic intramolecular Pd?Pd interaction was synthesized and thoroughly characterized. The synthesized benzothiazolepalladacycle directly anchored on SBA-15 to form an efficient heterogen
Oxidative Amidation of Amines in Tandem with Transamidation: A Route to Amides Using Visible-Light Energy
Nandi, Jyoti,Vaughan, Matthew Z.,Sandoval, Arturo León,Paolillo, Joshua M.,Leadbeater, Nicholas E.
, p. 9219 - 9229 (2020/08/14)
A methodology is reported for preparing amides using amines as an acyl source. The protocol involves the visible-light-promoted oxidative amidation of amines with pyrazole to synthesize N-acyl pyrazoles followed by transamidation. By combining photoredox catalysis with oxoammonium cations in the presence of sodium persulfate as a terminal oxidant, the N-acyl pyrazoles could be prepared efficiently and effectively using blue LEDs. The transamidation step was performed without the need to purify the N-acyl pyrazole intermediate, and a range of amides were generated in good to excellent yields.
Cobalt-catalyzed aminocarbonylation of (hetero)aryl halides promoted by visible light
Alexanian, Erik J.,Veatch, Alexander M.
, p. 7210 - 7213 (2020/07/23)
The catalytic aminocarbonylation of (hetero)aryl halides is widely applied in the synthesis of amides but relies heavily on the use of precious metal catalysis. Herein, we report an aminocarbonylation of (hetero)aryl halides using a simple cobalt catalyst under visible light irradiation. The reaction extends to the use of (hetero)aryl chlorides and is successful with a broad range of amine nucleophiles. Mechanistic investigations are consistent with a reaction proceeding via intermolecular charge transfer involving a donor-acceptor complex of the substrate and cobaltate catalyst.
Tert -Butyl nitrite promoted transamidation of secondary amides under metal and catalyst free conditions
Sureshbabu, Popuri,Azeez, Sadaf,Chaudhary, Priyanka,Kandasamy, Jeyakumar
, p. 845 - 850 (2019/01/30)
A mild and efficient method is demonstrated for the transamidation of secondary amides with various amines including primary, secondary, cyclic and acyclic amines in the presence of tert-butyl nitrite. The reaction proceeds through the N-nitrosamide intermediate and provides the transamidation products in good to excellent yields at room temperature. Moreover, the developed methodology does not require any catalyst or additives.
2,2-Diazido-1,2-diarylethanones: Synthesis and Reactivity with Primary Amines
Holzschneider, Kristina,H?ring, Andreas P.,Kirsch, Stefan F.
, p. 2824 - 2831 (2019/04/30)
We describe the synthesis and reactivity of a new class of diazidated compounds: the 2,2-diazido-1,2-diarylethanones. The diazides are easily accessible from 1,2-diarylethanones through a mild and simple protocol for the direct oxidative diazidation, using iodine and sodium azide in DMSO at room temperature. In studies towards their reactivity with amine nucleophiles under basic conditions, the diazides are shown to undergo a controlled fragmentation reaction that provides a straightforward access to the corresponding amides. In stark contrast to our previous results on the amine-triggered fragmentation of diazidated compounds, aromatic nitriles are found to be by-products of synthetic value. The net reaction consisting of diazidation and subsequent fragmentation, thus, provides a simple way to convert 1,2-diarylethanones into both aromatic amides and nitriles.
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.
A Visible-Light-Driven, Metal-free Route to Aromatic Amides via Radical Arylation of Isonitriles
Malacarne, Marco,Protti, Stefano,Fagnoni, Maurizio
supporting information, p. 3826 - 3830 (2017/11/15)
The photochemical metal-free carboamidation of aryl radicals has been exploited for the preparation of aromatic amides, including hetero- and polyaromatic derivatives, under visible light irradiation of arylazo sulfones in the presence of isocyanides in aqueous acetonitrile. The process was useful for the smooth preparation of the antidepressant moclobemide. (Figure presented.).
A high-efficient method for the amidation of carboxylic acids promoted by triphenylphosphine oxide and oxalyl chloride
Jiang, Lixue,Yu, Jing,Niu, Fanfan,Zhang, Derundong,Sun, Xiaoling
, (2017/03/08)
A effective amidation reaction of carboxylic acids with various amines promoted by triphenylphosphine oxide and oxalyl chloride under mild and neutral conditions has been developed. The feature of this procedure was the using and recycling of triphenylphosphine oxide at room temperature in 0.5?h. Furthermore a plausible mechanism also be deduced with the help of 31P NMR spectroscopy.
