4329-81-1Relevant articles and documents
Effect of the ancillary ligand in N-heterocyclic carbene iridium(III) catalyzed N-alkylation of amines with alcohols
Feng, Xinshu,Huang, Ming
, (2021/06/21)
A series of air-stable N-heterocyclic carbene (NHC) Ir(III) complexes (Ir1-6), bearing various combinations of chlorine, pyridine and NHC ligands, were assayed for the N-alkylation of amines with alcohols. It was found that Ir3, with two monodentate 1,3-bis-methyl-imidazolylidene (IMe) ligands, emerged as the most active complex. A large variety of amines and primary alcohols were efficiently converted into mono-N-alkylated amines in 53–96% yields. As a special highlight, for the challenging MeOH, selective N-monomethylation could be achieved using KOH as a base under an air atmosphere. Moreover, this catalytic system was successfully applied to the gram-scale synthesis of some valuable compounds.
Synthesis of an Fe-Pd bimetallic catalyst for: N -alkylation of amines with alcohols via a hydrogen auto-transfer methodology
Wu, Peng-Yu,Lu, Guo-Ping,Cai, Chun
, p. 396 - 404 (2021/01/28)
Hydrogen auto-transfer (HAT) or borrowing hydrogen (BH) methodology which combines dehydrogenation, intermediate reaction and hydrogenation, is recognized as an excellent strategy for one-pot synthesis from an economic and environmental point of view. Although much effort has been made on the development of catalysts for HAT reactions, harsh conditions, external base or large amounts of noble metals are still required in most reported catalysis systems, and thus the exploration of a highly efficient and recyclable heterogeneous catalyst remains meaningful. In this work, a novel bimetallic catalyst, Fe10Pd1/NC500 derived from bimetallic MOF NH2-MIL-101(Fe10Pd1), has been prepared, and the catalyst exhibits superior catalytic performance for the N-alkylation of amines with alcohols via a hydrogen auto-transfer methodology. High yields of the desired products were achieved at 120 °C with an alcohol/amine molar ratio of 2?:?1 and required no external additive or solvent. A distinct enhancement in catalytic performance is observed when compared with monometallic catalysts, which can be ascribed to the "synergistic effects"inside the bimetallic alloys. The N-doped carbon support has been revealed to provide the necessary basicity which avoids the requirement of an external base. Moreover, a wide substrate range and remarkable reusability have been shown by Fe10Pd1/NC500, and this work highlights new possibilities for bimetallic catalysts applied in sustainable chemistry.
Convenient and Reusable Manganese-Based Nanocatalyst for Amination of Alcohols
Subaramanian, Murugan,Ramar, Palmurukan M.,Sivakumar, Ganesan,Kadam, Ravishankar G.,Petr, Martin,Zboril, Radek,Gawande, Manoj B.,Balaraman, Ekambaram
, p. 4334 - 4341 (2021/08/25)
The development of new sustainable nanocatalytic systems for green chemical synthesis is a growing area in chemical science. Herein, a reusable heterogeneous N-doped graphene-based manganese nanocatalyst (Mn@NrGO) for selective N-alkylation of amines with alcohols is described. Mechanistic studies illustrate that the catalytic reaction follows a domino dehydrogenation-condensation-hydrogenation sequence of alcohols and amines with the formation of water as the sole by-product. The scope of the reaction is extended to the synthesis of pharmaceutically important N-alkylated amine intermediates. The heterogeneous nature of the catalyst made it easy to separate for long-term performance, and the recycling study revealed that the catalyst was robust and retained its activity after several recycling experiments.
Ruthenium(ii) complexes with N-heterocyclic carbene-phosphine ligands for theN-alkylation of amines with alcohols
Huang, Ming,Li, Yinwu,Lan, Xiao-Bing,Liu, Jiahao,Zhao, Cunyuan,Liu, Yan,Ke, Zhuofeng
supporting information, p. 3451 - 3461 (2021/05/03)
Metal hydride complexes are key intermediates forN-alkylation of amines with alcohols by the borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols and the hydrogenation of imines. Herein we report ruthenium(ii) complexes with hetero-bidentate N-heterocyclic carbene (NHC)-phosphine ligands, which realize smart pathway selection in theN-alkylated reactionviareactivity tuning of [Ru-H] species by hetero-bidentate ligands. In particular, complex6cbwith a phenyl wingtip group and BArF?counter anion, is shown to be one of the most efficient pre-catalysts for this transformation (temperature is as low as 70 °C, neat conditions and catalyst loading is as low as 0.25 mol%). A large variety of (hetero)aromatic amines and primary alcohols were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields. Notably, aliphatic amines, challenging methanol and diamines could also be transformed into the desired products. Detailed control experiments and density functional theory (DFT) calculations provide insights to understand the mechanism and the smart pathway selectionvia[Ru-H] species in this process.
Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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Paragraph 0086-0091; 0094, (2021/05/29)
The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
Catalyst- And solvent-free efficient access to: N -alkylated amines via reductive amination using HBpin
Bauri, Somnath,Pandey, Vipin K.,Rit, Arnab
supporting information, p. 3853 - 3857 (2020/07/27)
A sustainable approach which works under catalyst- and solvent-free conditions for the synthesis of structurally diverse secondary amines has been uncovered. This one-pot protocol works efficiently at room temperature and is compatible with a wide range of sterically and electronically diverse aldehydes and primary amines. Notably, this simple process offers scalability, excellent functional group tolerance, chemoselectivity, and is also effective at the synthesis of biologically relevant molecules. This journal is
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.
Thioglycerol-Stabilized Rhodium Nanoparticles in Biphasic Medium as Catalysts in Multistep Reactions
Guerrero-Ríos, Itzel,Portales-Martínez, Benjamín,Reina, Antonio,Serrano-Maldonado, Alejandro
supporting information, (2020/07/04)
Small rhodium nanoparticles (ca. 3.5 nm) were prepared by the decomposition of an organometallic precursor under hydrogen pressure in glycerol using 1-thioglycerol as stabilizer. Full characterization in the solid state [HR-TEM, EDX, XPS] showed a fcc structure for the Rh0/RhI nanoparticles capped with thiolate ligand. Reduction of different functionalities, including nitro groups and imines, was applied to tandem reductive amination of aldehydes with primary and secondary amines, and to the synthesis of N-substituted anilines from nitrobenzene. In addition, thiolate-capped RhNPs could be recovered and reused up to 5 runs without loss of activity nor selectivity.
Efficient One-Pot Reductive Aminations of Carbonyl Compounds with Aquivion-Fe as a Recyclable Catalyst and Sodium Borohydride
Airoldi, Veronica,Piccolo, Oreste,Roda, Gabriella,Appiani, Rebecca,Bavo, Francesco,Tassini, Riccardo,Paganelli, Stefano,Arnoldi, Sebastiano,Pallavicini, Marco,Bolchi, Cristiano
supporting information, p. 162 - 168 (2019/12/11)
A one-pot reductive amination of aldehydes and ketones with NaBH4 was developed with a view to providing efficient, economical and greener synthetic conditions. A recyclable iron-based Lewis catalyst, Aquivion-Fe, was used to promote imine formation in cyclopentyl methyl ether, followed by the addition of a small amount of methanol to the reaction mixture to enable C=N reduction by NaBH4. The protocol, applied to a wide number of amines and carbonyl compounds, resulted in ever complete conversion of these latter with excellent chemoselectivity towards the expected amination products in the most cases. Isolated yields, determined for a selection of the screened substrates, were found consistent with the previously obtained conversion and selectivity data. Cinacalcet, an important active pharmaceutical ingredient, was efficiently prepared by the title procedure.
Nickel(II)-NΛNΛO Pincer Type Complex-Catalyzed N-alkylation of Amines with Alcohols via the Hydrogen Autotransfer Reaction
Balamurugan, Gunasekaran,Ramesh, Rengan,Malecki, Jan Grzegorz
, p. 7125 - 7135 (2020/06/08)
A highly sustainable catalytic protocol for the coupling of alcohols and amines for selective monoalkylated amines using Ni(II)-NΛNΛO pincer type complexes through the borrowing hydrogen methodology is described. An array of Ni(II) catalysts (1-3) was synthesized and characterized by various spectral and analytical methods. Furthermore, the distorted square planar geometry of the complexes (1 and 2) was substantiated with single crystal X-ray diffraction study. The inexpensive nickel-based catalytic methodology displays a broad substrate scope for the N-alkylation of aromatic and heteroaromatic amines using a diverse range of primary alcohols with excellent yields up to 97%. The present approach is environmentally benign, which liberates water as the sole byproduct. A short synthesis of drug intermediates such as mepyramine and chloropyramine illustrates the utility of the present protocol.
