527-85-5Relevant academic research and scientific papers
Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
Yi, Jaeeun,Kim, Hyun Tae,Jaladi, Ashok Kumar,An, Duk Keun
supporting information, p. 129 - 132 (2021/11/17)
Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
Nitrogen Atom Transfer Catalysis by Metallonitrene C?H Insertion: Photocatalytic Amidation of Aldehydes
Schmidt-R?ntsch, Till,Verplancke, Hendrik,Lienert, Jonas N.,Demeshko, Serhiy,Otte, Matthias,Van Trieste, Gerard P.,Reid, Kaleb A.,Reibenspies, Joseph H.,Powers, David C.,Holthausen, Max C.,Schneider, Sven
, (2022/01/20)
C?H amination and amidation by catalytic nitrene transfer are well-established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C?H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd?N) with a diradical nitrogen ligand that is singly bonded to PdII. Despite the subvalent nitrene character, selective C?H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3SiMe3. Based on these results, a photocatalytic protocol for aldehyde C?H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C?H nitrogen atom transfer offers facile access to primary amides after deprotection.
Ru(ii)- And Ru(iv)-dmso complexes catalyze efficient and selective aqueous-phase nitrile hydration reactions under mild conditions
Dubey, Santosh Kumar,Kaur, Gurmeet,Rath, Nigam P.,Trivedi, Manoj
, p. 17339 - 17346 (2021/10/08)
New water-soluble ruthenium(ii)- and ruthenium(iv)-dmso complexes [RuCl2(dmso)2(NH3)(CH3CN)] (1), [RuCl2(dmso)3(CH3CN)] (2), and [RuCl2(dmso)3(NH3)]·PF6·Cl (3) have been synthesized and characterized using elemental analyses, IR, 1H and 31P NMR, and electronic absorption spectroscopy. The molecular structures of complexes 1-3 were determined crystallographically. The reactivity of complexes 1-3 has been tested for aqueous-phase nitrile hydration at 60 °C in air, and good efficiency and selectivity are shown for the corresponding amide derivatives. Best performance is achieved with complex 3. Amide conversions of 56-99% were obtained with a variety of aromatic, alkyl, and vinyl nitriles. The reaction tolerated hydroxyl, nitro, bromo, formyl, pyridyl, benzyl, alkyl, and olefinic functional groups. Amides were isolated by simple decantation from the aqueous-phase catalyst. A catalyst loading down to 0.0001 mol% was examined and turnover numbers as high as 990?000 were observed. The catalyst was stable for weeks in solution and could be reused more than seven times without significant loss in catalytic activity. The gram-scale reaction was also performed to produce the desired product in high yields. This journal is
INTERMEDIATES AND METHODS FOR THE PREPARATION OF TOLVAPTAN AND ITS DERIVATIVES
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Page/Page column 30, (2021/12/31)
The present invention relates to new intermediates for the synthesis of tolvaptan and its derivatives, as well as a method for its preparation involving said intermediates.
Visible light-mediated synthesis of amides from carboxylic acids and amine-boranes
Chen, Xuenian,Kang, Jia-Xin,Ma, Yan-Na,Miao, Yu-Qi
supporting information, p. 3595 - 3599 (2021/06/06)
Here, a photocatalytic deoxygenative amidation protocol using readily available amine-boranes and carboxylic acids is described. This approach features mild conditions, moderate-to-good yields, easy scale-up, and up to 62 examples of functionalized amides with diverse substituents. The synthetic robustness of this method was also demonstrated by its application in the late-stage functionalization of several pharmaceutical molecules.
Half-Sandwich Iridium Complexes Based on β-Ketoamino Ligands: Preparation, Structure, and Catalytic Activity in Amide Synthesis
Wang, Yang,Guo, Wen,Guan, Ai-Lin,Liu, Shuang,Yao, Zi-Jian
, p. 11514 - 11520 (2021/07/31)
A series of β-ketoamino-based N,O-chelate half-sandwich iridium complexes with the general formula [Cp*IrClL] have been prepared in good yields. These air-insensitive iridium complexes showed desirable catalytic activity in an amide preparation under mild conditions. A number of amides with diverse substituted groups were furnished in a one-pot reaction with good-to-excellent yields through an amidation reaction of NH2OH·HCl with aldehydes in the presence of these iridium(III) precursors. The excellent catalytic activity, mild reaction conditions, and broad substrate scope gave this type of iridium catalyst potential for use in industry. All of the obtained iridium complexes were well characterized by different spectroscopy techniques. The exact molecular structure of complex 3 has been confirmed by single-crystal X-ray analysis.
Nano-construction of CuO nanorods decorated with g-C3N4 nanosheets (CuO/g-C3N4-NS) as a superb colloidal nanocatalyst for liquid phase C[sbnd]H conversion of aldehydes to amides
Mohammadi, Robabeh,Gholipour, Behnam,Alamgholiloo, Hassan,Rostamnia, Sadegh,Mohtasham, Hamed,Zonouzi, Afsaneh,Ramakrishna, Seeram,Shokouhimehr, Mohammadreza
, (2021/04/27)
Herein, we describe an intelligent strategy to fabricate nanosheets of graphitic carbon nitride (g-C3N4) decorated with nanorods copper oxide (CuO NRs). Then, the catalytic activity of CuONRs/g-C3N4-NS was developed for the synthesis of primary amides in water. The morphology of CuO and its synergetics effect with nanosheets g-C3N4 a major role in the yield of products. Furthermore, hydroxylamine hydrochloride (NH2OH·HCl) due to availability and affordability was used as a suitable substitute for ammonia source. The findings demonstrate that this layer nanostructure is a superb catalyst for converting various derivatives of aldehyde to their corresponding amides. The current protocol can be useful criterion in the synthesis and stabilization of metal oxides and provides new insight in organic transformation.
Efficient nitriding reagent and application thereof
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Paragraph 0315-0317, (2021/03/31)
The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
Catalyst, preparation method thereof and preparation method of amide compound
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Paragraph 0142-0146, (2020/01/12)
The invention relates to a catalyst, a preparation method thereof, and a preparation method for hydrating nitrile groups into amides. The catalyst is used for catalyzing nitrile groups to be hydratedinto amides, and the structural general formula of the catalyst is shown in the specification. In the formula, a plurality of R are respectively and independently ones selected from aromatic groups, heteroaromatic groups and non-aromatic ring groups; a plurality of R are ones respectively and independently selected from linear alkyl groups and alkane aromatic groups; X is one selected from Cl and Br; and L is one selected from OTf, BF4, PF6 and SbF6. The catalyst can catalyze nitrile groups to be hydrated into amides, and the nitrile groups can be catalyzed to be hydrated into amides even at a low temperature (20-80 DEG C); besides, compared with existing common catalysts for catalyzing nitrile groups to be hydrated into amides, the catalyst has the advantages that the equivalent weight of the catalyst can be obviously reduced, and nitrile groups can reach a relatively high conversion rate when the equivalent weight of the catalyst is only 0.01 mol%-0.5 mol%; and meanwhile, the catalyst is wider in application range and can catalyze various nitrile compounds to be hydrated into amide compounds.
Arene-ruthenium(II)-phosphine complexes: Green catalysts for hydration of nitriles under mild conditions
Vyas, Komal M.,Mandal, Poulami,Singh, Rinky,Mobin, Shaikh M.,Mukhopadhyay, Suman
, (2019/12/11)
Three new arene-ruthenium(II) complexes were prepared by treating [{RuCl(μ-Cl)(η6-arene)}2] (η6-arene = p-cymene) dimer with tri(2-furyl)phosphine (PFu3) and 1,3,5-triaza-7-phosphaadamantane (PTA), respectively to obtain [RuCl2(η6-arene)PFu3] [Ru]-1, [RuCl(η6-arene)(PFu3)(PTA)]BF4 [Ru]-2 and [RuCl(η6-arene)(PFu3)2]BF4 [Ru]-3. All the complexes were structurally identified using analytical and spectroscopic methods including single-crystal X-ray studies. The effectiveness of resulting complexes as potential homogeneous catalysts for selective hydration of different nitriles into corresponding amides in aqueous medium and air atmosphere was explored. There was a remarkable difference in catalytic activity of the catalysts depending on the nature and number of phosphorus-donor ligands and sites available for catalysis. Experimental studies performed using structural analogues of efficient catalyst concluded a structural-activity relationship for the higher catalytic activity of [Ru]-1, being able to convert huge variety of aromatic, heteroaromatic and aliphatic nitriles. The use of eco-friendly water as a solvent, open atmosphere and avoidance of any organic solvent during the catalytic reactions prove the reported process to be truly green and sustainable.
