1739-02-2Relevant academic research and scientific papers
Use of a Droplet Platform to Optimize Pd-Catalyzed C-N Coupling Reactions Promoted by Organic Bases
Baumgartner, Lorenz M.,Dennis, Joseph M.,White, Nicholas A.,Buchwald, Stephen L.,Jensen, Klavs F.
, p. 1594 - 1601 (2019)
Recent advances in Pd-catalyzed carbon-nitrogen cross-coupling have enabled the use of soluble organic bases instead of insoluble or strong inorganic bases that are traditionally employed. The single-phase nature of these reaction conditions facilitates their implementation in continuous flow systems, high-throughput optimization platforms, and large-scale applications. In this work, we utilized an automated microfluidic optimization platform to determine optimal reaction conditions for the couplings of an aryl triflate with four types of commonly employed amine nucleophiles: anilines, amides, primary aliphatic amines, and secondary aliphatic amines. By analyzing trends in catalyst reactivity across different reaction temperatures, base strengths, and base concentrations, we have developed a set of general recommendations for Pd-catalyzed cross-coupling reactions involving organic bases. The optimization algorithm determined that the catalyst supported by the dialkyltriarylmonophosphine ligand AlPhos was the most active in the coupling of each amine nucleophile. Furthermore, our automated optimization revealed that the phosphazene base BTTP can be used to facilitate the coupling of secondary alkylamines and aryl triflates.
Catalytic Amination of Phenols with Amines
Chen, Kai,Kang, Qi-Kai,Li, Yuntong,Wu, Wen-Qiang,Zhu, Hui,Shi, Hang
supporting information, p. 1144 - 1151 (2022/02/05)
Given the wide prevalence and ready availability of both phenols and amines, aniline synthesis through direct coupling between these starting materials would be extremely attractive. Herein, we describe a rhodium-catalyzed amination of phenols, which provides concise access to diverse anilines, with water as the sole byproduct. The arenophilic rhodium catalyst facilitates the inherently difficult keto–enol tautomerization of phenols by means of π-coordination, allowing for the subsequent dehydrative condensation with amines. We demonstrate the generality of this redox-neutral catalysis by carrying out reactions of a large array of phenols with various electronic properties and a wide variety of primary and secondary amines. Several examples of late-stage functionalization of structurally complex bioactive molecules, including pharmaceuticals, further illustrate the potential broad utility of the method.
CuI/2-Aminopyridine 1-Oxide Catalyzed Amination of Aryl Chlorides with Aliphatic Amines
Chen, Xiahong,He, Yongqiang,Liang, Yun,Liu, Wenjie,Wang, Deping,Xia, Xiaohong,Xu, Jiamin,Xu, Zhifeng,Zhang, Fuxing,Zhang, Xin
supporting information, p. 7486 - 7490 (2020/10/12)
A class of 2-aminopyridine 1-oxides are discovered to be effective ligands for the Cu-catalyzed amination of less reactive (hetero)aryl chlorides. A wide range of functionalized (hetero)aryl chlorides reacted with various aliphatic amines to afford the desired products in good to excellent yields under the catalyst of CuI/2-aminopyridine 1-oxides. Furthermore, the catalyst system worked well for the coupling of cyclic secondary amines and N-methyl benzylamine with (hetero)aryl chlorides.
Nickelous imine complex with nickel nitrogen double-bond structure and preparation and application of nickelous imine complex
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Paragraph 0034-0037, (2019/10/01)
The invention relates to a nickelous imine complex with a nickel nitrogen double-bond structure and preparation and application of the nickelous imine complex. The preparation method of the nickelousimine complex comprises the following steps that 1, a phenyldipyridine ligand solution is added into a zero-valent nickel precursor solution for a reaction for 3-5 hours at room temperature; 2, azidobenzene is added for a reaction for 2-5 hours at room temperature, and through aftertreatment, the nickelous imine complex is obtained. The nickelous imine complex is used for catalyzing an anti-Markovnikov hydroamination reaction of styrene to prepare a linear-chain amine compound. Compared with the prior art, the synthesizing technology is simple and green, the selectivity and the yield are high,the nickelous imine complex prepared by using the method has the advantages of stable physicochemical properties, thermal stability and the like, and the nickelous imine complex can show excellent activity and regioselectivity in the reaction of catalyzing the anti-Markovnikov hydroamination reaction of the styrene.
Nitrogen-iridium [...] imine complexes of multiple bond, preparation method and application thereof (by machine translation)
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Paragraph 0033; 0034; 0035, (2019/02/13)
The invention belongs to the technical field of synthetic chemistry, in particular to a multiple bond of nitrogen-iridium [...] imine complex, preparation method and its application. The invention relates to a compound cyclooctadiene [...][...] dimer [IrCl (COD)]2 As the raw material, it is connected to the phenyl pyrrole compounds in the reaction under alkaline conditions, obtain [...] complex containing a precursor, then the use of azide oxidation process will be its oxidized into nitrogen-iridium [...] imine compound of the multiple bond. The invention synthesis technique is simple green, has excellent selectivity and high yield. The invention of [...] imine complex with stable physical and chemical properties and characteristics such as thermal stability, and in the hydroamination reaction of olefins demonstrate the excellent activity and regional selective (counter-ma rules). (by machine translation)
Preparation of large-steric-hindrance trivalent rhodium imide complex and application thereof
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Paragraph 0031; 0032; 0033, (2019/04/30)
The invention provides a large-steric-hindrance trivalent rhodium imide complex containing a rhodium-nitrogen dual-key structure. The large-steric-hindrance trivalent rhodium imide complex is characterized by including the following structure shown in the description. A synthesis technology is simple and green, and has excellent selectivity and a high yield. The large-steric-hindrance trivalent rhodium imide complex has the features of stable physical and chemical properties and thermal stability, and has excellent activity and regional selectivity in an anti-Markovnikov hydroamination reaction of olefins.
Regiospecific N-Arylation of Aliphatic Amines under Mild and Metal-Free Reaction Conditions
Purkait, Nibadita,Kervefors, Gabriella,Linde, Erika,Olofsson, Berit
supporting information, p. 11427 - 11431 (2018/08/28)
A transition metal-free N-arylation of primary and secondary amines with diaryliodonium salts is presented. Both acyclic and cyclic amines are well tolerated, providing a large set of N-alkyl anilines. The methodology is unprecedented among metal-free methods in terms of amine scope, the ability to transfer both electron-withdrawing and electron-donating aryl groups, and efficient use of resources, as excess substrate or reagents are not required.
Reinvestigating Raney nickel mediated selective alkylation of amines with alcohols via hydrogen autotransfer methodology
Mehta, Astha,Thaker,Londhe,Nandan, Santosh R.
, p. 241 - 251 (2014/05/20)
An efficient, cost-effective use of Raney nickel (R-Ni) a widely used industrial catalyst for N-alkylation using alcohols is highlighted here. The work describes the scope and capability of R-Ni in hydrogen autotransfer reactions enabling its widespread use in the Chemical and Pharmaceutical industry. R-Ni of W4, T4, and W7 grades were prepared and evaluated for alkylation of amines. The best activity and selectivity for mono alkylation of amines were obtained using W4 R-Ni at 1:4 moles of amine to alcohol in xylene at reflux. T4 R-Ni also showed ability to form stable imines. The prepared R-Ni was also recycled and reused for N-alkylation reaction. The optimized methodology was applied for synthesis of Active Pharmaceutical ingredients Piribedil and Mepyramine. The simplicity and wide substrate scope makes this method a preferred Hydrogen Auto-transfer protocol for the alkylation of amines.
Reductive N-alkylation of nitro compounds to N -Alkyl and N, N -dialkyl amines with glycerol as the hydrogen source
Cui, Xinjiang,Deng, Youquan,Shi, Feng
, p. 808 - 811 (2013/06/27)
As the sustainable and promising hydrogen source, here, glycerol was directly used as the hydrogen source for the reductive amination of alcohol using nitrobenzene as the starting material. The amination of alcohols, especially aliphatic alcohols with different structures, was realized, and mono- or disubstituted amines were synthesized with excellent yields. The reaction mechanism was also explored.
Direct reductive amination of aldehydes catalyzed by carbon nanotube/gold nanohybrids
Kumar, Rahul,Gravel, Edmond,Hagege, Agnes,Li, Haiyan,Verma, Deepti,Namboothiri, Irishi N. N.,Doris, Eric
, p. 3571 - 3575 (2014/01/06)
Gold digger: The direct reductive amination of aldehydes catalyzed by gold/carbon-nanotube nanohybrids with a silane as a hydride source is reported. Copyright
