- Design and Atroposelective Construction of IAN analogues by Organocatalytic Asymmetric Heteroannulation of Alkynes
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An organocatalytic atroposelective strategy for accessing enantioenriched axially chiral IAN analogues was developed for the first time. A class of novel atropisomeric C2-arylquinoline skeletons were synthesized with high enantiocontrol via chiral phosphoric-acid-catalyzed heteroannulation of in situ generated vinylidene ortho-quinone methide (VQM) intermediates with ortho-aminophenones. The strategy tolerated a broad substrate scope, providing a facile organocatalytic approach to IAN analogues in good yields and excellent enantioselectivities under mild reaction conditions. Moreover, the synthetic utility of this methodology was illustrated through further transformations into IAN-type ligand and axially chiral thiourea.
- Shen, Jiahua,Tan, Bin,Wang, Yong-Bin,Wu, San,Zhang, Lei,Zhong, Guofu
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- Tungsten-Catalyzed Direct N-Alkylation of Anilines with Alcohols
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The implementation of non-noble metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of non-noble metal catalysts. Herein, we report a tungsten-catalyzed N-alkylation reaction of anilines with primary alcohols via BH/HA. This phosphine-free W(phen)(CO)4 (phen=1,10-phenthroline) system was demonstrated as a practical and easily accessible in-situ catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.
- Lan, Xiao-Bing,Ye, Zongren,Yang, Chenhui,Li, Weikang,Liu, Jiahao,Huang, Ming,Liu, Yan,Ke, Zhuofeng
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p. 860 - 865
(2021/01/18)
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- Cooperative catalysis of molybdenum with organocatalysts for distribution of products between amines and imines
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Multi-amino groups and nitrogen donors compound was discovered as an organocatalyst for N-alkylation of alcohols with amines in the presence of Mo(CO)6. The Mo(CO)6/organocatalyst binary system has shown to be a highly active catalyst for the N-alkylation reaction between alcohols and amines with excellent tolerance of variable starting materials bearing different functional groups. Of particular note, this method possessing a superiority selectivity in the synthesis of N-alkylated amines or imines, which can be controlled by the reaction temperature. The cooperative catalysis mechanism in combination of Mo(CO)6 with organocatalyst was elucidated by control experiments.
- Wu, Di,Bu, Qingqing,Guo, Cheng,Dai, Bin,Liu, Ning
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- Ruthenium(ii) complexes with N-heterocyclic carbene-phosphine ligands for theN-alkylation of amines with alcohols
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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.
- Huang, Ming,Li, Yinwu,Lan, Xiao-Bing,Liu, Jiahao,Zhao, Cunyuan,Liu, Yan,Ke, Zhuofeng
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supporting information
p. 3451 - 3461
(2021/05/03)
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- Effect of the ancillary ligand in N-heterocyclic carbene iridium(III) catalyzed N-alkylation of amines with alcohols
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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.
- Feng, Xinshu,Huang, Ming
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- Synthesis of an Fe-Pd bimetallic catalyst for: N -alkylation of amines with alcohols via a hydrogen auto-transfer methodology
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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.
- Wu, Peng-Yu,Lu, Guo-Ping,Cai, Chun
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p. 396 - 404
(2021/01/28)
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- Silver/manganese dioxide nanorod catalyzed hydrogen-borrowing reactions and tert-butyl ester synthesis
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Silver/manganese dioxide (Ag@MnO2) nanorods are synthesized and characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray powder diffraction, and X-ray photoelectron spectroscopy. It was discovered that Ag@MnO2 nanorods can realize hydrogen-borrowing reactions in high yields and are also effective for the synthesis of tert-butyl esters from aryl cyanides and tert-butyl hydroperoxide in a short period of time. Mechanistic experiments revealed that this catalytic system acts as a Lewis acid in hydrogen-borrowing reactions, while the synthesis of tert-butyl esters occurs through a radical pathway. This is the first report on the excellent catalytic activity of Ag@MnO2 nanorods as a catalyst.
- Luo, Huanhuan,Wang, Dawei,Xu, Zhaojun,Yang, Bobin,Yang, Yike
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p. 708 - 715
(2021/03/03)
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- Convenient and Reusable Manganese-Based Nanocatalyst for Amination of Alcohols
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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.
- Subaramanian, Murugan,Ramar, Palmurukan M.,Sivakumar, Ganesan,Kadam, Ravishankar G.,Petr, Martin,Zboril, Radek,Gawande, Manoj B.,Balaraman, Ekambaram
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p. 4334 - 4341
(2021/08/25)
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- Switchable Imine and Amine Synthesis Catalyzed by a Well-Defined Cobalt Complex
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Switchable imine and amine synthesis catalyzed by a tripodal ligand-supported well-defined cobalt complex is presented herein. A large variety of primary alcohols and amines were selectively converted to imines or amines in good to excellent yields. It is discovered that the base plays a crucial role on the selectivity. A catalytic amount of base leads to the imine formation, while an excess loading of base results in the amine product. This strategy on product selectivity also strongly depends on the organometallic catalysts in use. We expect that the present study could provide useful insights toward selective organic synthesis and catalyst design.
- Paudel, Keshav,Xu, Shi,Hietsoi, Oleksandr,Pandey, Bedraj,Onuh, Chuka,Ding, Keying
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supporting information
p. 418 - 426
(2021/02/01)
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- Mechanistic Insights into the FeCl3-Catalyzed Oxidative Cross-Coupling of Phenols with 2-Aminonaphthalenes
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The selective FeCl3-catalyzed oxidative cross-coupling reaction between phenols and primary, secondary, and tertiary 2-aminonaphthalene derivatives was investigated. The generality of this scalable method provides a sustainable alternative for preparing N,O-biaryl compounds that are widely used as ligands and catalysts. Based on a comprehensive kinetic investigation, a catalytic cycle involving a ternary complex that binds to both the coupling partners and the oxidant during the key oxidative coupling step is postulated. Furthermore, the studies showed that the reaction is regulated by off-cycle acid-base and ligand exchange processes.
- Vershinin, Vlada,Forkosh, Hagit,Ben-Lulu, Mor,Libman, Anna,Pappo, Doron
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- Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation
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A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]
- Wang, Erfei,Chen, Kaixuan,Chen, Yinan,Zhang, Jiawei,Lin, Xinrong,Chen, Mao
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- Scalable preparation of stable and reusable silica supported palladium nanoparticles as catalysts for N-alkylation of amines with alcohols
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The development of nanoparticles-based heterogeneous catalysts continues to be of scientific and industrial interest for the advancement of sustainable chemical processes. Notably, up-scaling the production of catalysts to sustain unique structural features, activities and selectivities is highly important and remains challenging. Herein, we report the expedient synthesis of Pd-nanoparticles as amination catalysts by the reduction of simple palladium salt on commercial silica using molecular hydrogen. The resulting Pd-nanoparticles constitute stable and reusable catalysts for the synthesis of various N-alkyl amines using borrowing hydrogen technology without the use of any base or additive. By applying this Pd-based catalyst, functionalized and structurally diverse N-alkylated amines as well as some selected drug molecules were synthesized in good to excellent yields. Practical and synthetic utility of this Pd-based amination protocol has been demonstrated by upscaling catalyst preparation and amination reactions to several grams-scales as well as recycling of catalyst. Noteworthy, this Pd-catalyst preparation has been up-scaled to kilogram scale and catalysts prepared in both small (1 g) and large-scale (kg) exhibited similar structural features and activity.
- Alshammari, Ahmad S.,Natte, Kishore,Kalevaru, Narayana V.,Bagabas, Abdulaziz,Jagadeesh, Rajenahally V.
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p. 141 - 149
(2020/01/06)
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- Mono/Dual Amination of Phenols with Amines in Water
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We herein describe a practical direct amination of phenols through a palladium-catalyzed hydrogen-transfer-mediated activation method to synthesize the secondary and tertiary amines. In this conversion, environmentally friendly water and inexpensive ammonium formate were used as solvent and reductant, respectively. A range of amines, including aliphatic amines, aniline, secondary amines, and diamines, could be coupled effectively by this method to achieve mono/dual amination and cyclization of phenols. This study not only provides a green and mild strategy for the synthesis of secondary and tertiary naphthylamines but also expands the synthesis of chloroquine in organic chemistry.
- Liang, Wanyi,Xie, Feng,Yang, Zhihai,Zeng, Zheng,Xia, Chuanjiang,Li, Yibiao,Zhu, Zhongzhi,Chen, Xiuwen
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supporting information
p. 8291 - 8295
(2020/10/12)
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- Thiazoline-Iridium (III) Complexes and Immobilized Nanomaterials as Selective Catalysts in N-Alkylation of Amines with Alcohols
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In this research, a new series of thiazoline-iridium (III) complexes (4–7) derived from cysteine were prepared and fully characterized by conventional methods. The molecular structure of complex 5 was also determined by single-crystal X-ray diffraction. These complexes were evaluated as catalysts for hydrogen-borrowing reactions of amines with alcohols. In particular, complex 5 showed the best activity as catalyst. Various amines have been alkylated with alcohols affording moderate to good yield (33–99%). Moreover, the immobilized nanomaterials (M1,2) were fabricated by sonication process from the best catalyst 5 with the multi-walled carbon nanotubes (MWCNTs) and graphene oxide (GO), respectively, and characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX) spectroscopy, and inductively coupled plasma-mass spectrometry (ICP-MS). The M1,2 nanomaterials were also tested as catalysts in model catalytic reaction for N-alkylation. The M1 nanomaterial showed significantly higher activity than the M2 nanomaterial. The M1 catalyst was recovered by filtration and reused for four catalytic cycles with high conversion (99%, 97%, 96%, and 86%).
- Denizalt?, Serpil,Dayan, Serkan,Günnaz, Salih,?ahin, Ertan
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- Room temperature N-heterocyclic carbene manganese catalyzed selective N-alkylation of anilines with alcohols
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The first example of room temperature non-noble metal homogeneous system catalyzed selective N-alkylation of anilines with alcohols by a bis-NHC manganese complex is presented. This system was applied to a large range of alcohols and anilines, including biologically relevant motifs and challenging methanol. Experimental and computational studies suggest an outer-sphere mechanism for this NHC-Mn system.
- Huang, Ming,Li, Yukui,Li, Yinwu,Liu, Jiahao,Shu, Siwei,Liu, Yan,Ke, Zhuofeng
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supporting information
p. 6213 - 6216
(2019/06/07)
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- Five-Coordinate Low-Spin {FeNO}7 PNP Pincer Complexes
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The synthesis and characterization of air-stable cationic mono nitrosonium Fe(I) PNP pincer complexes of the type [Fe(PNP)(NO)Cl]+ are described. These complexes are obtained via direct nitroslyation of [Fe(PNP)Cl2] with nitric oxide at ambient pressure. On the basis of magnetic and EPR measurements as well as DFT calculations, these compounds were found to adopt a low-spin d7 configuration and feature a nearly linear bound NO ligand suggesting FeINO+ rather than FeIINO? character. X-ray structures of all nitrosonium Fe(I) PNP complexes are presented. Preliminary investigations reveal that [Fe(PNPNH-iPr)(NO)(Cl)]+ efficiently catalyzes the conversion of primary alcohols and aromatic and benzylic amines to yield mono N-alkylated amines in good isolated yields.
- Pecak, Jan,St?ger, Berthold,Mastalir, Matthias,Veiros, Luis F.,Ferreira, Liliana P.,Pignitter, Marc,Linert, Wolfgang,Kirchner, Karl
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p. 4641 - 4646
(2019/03/29)
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- A bifunctional strategy for N-heterocyclic carbene-stabilized iridium complex-catalyzed: N -alkylation of amines with alcohols in aqueous media
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Through the strategy of combining bifunctional 2-hydroxypyridine and a thermally stable N-heterocyclic carbene ligand, an Ir-catalyzed N-monoalkylation reaction has been developed in aqueous media under base-free conditions. This reaction proceeds smoothly with high yields of various aromatic amines and sulfonamides with a wide range of primary alcohols. Experimental and computational studies revealed a metal-ligand cooperative mechanism and its thermal stability during the bifunctional catalysis in aqueous media.
- Huang, Ming,Li, Yinwu,Liu, Jiahao,Lan, Xiao-Bing,Liu, Yan,Zhao, Cunyuan,Ke, Zhuofeng
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supporting information
p. 219 - 224
(2019/01/28)
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- Palladium-catalyzed c(sp2)-n bond cross-coupling with triaryl phosphates
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The first general palladium-catalyzed amination of aryl phosphates is described. The combination of MorDalPhos with [Pd(-cinnamyl)Cl]2 enables the amination of electron-rich, electron-neutral, and electron-poor aryl phosphates with a board range of aromatic, aliphatic, and heterocyclic amines. Common functional groups such as ether, keto, ester, and nitrile show an excellent compatibility in this reaction condition. The solvent-free amination reactions are also successful in both solid coupling partners. The gram-scale cross-coupling is achieved by this catalytic system.
- Chen, Zicong,Chen, Xiangmeng,So, Chau Ming
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- Palladium-Catalyzed C(sp2)-N Bond Cross-Coupling with Triaryl Phosphates
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The first general palladium-catalyzed amination of aryl phosphates is described. The combination of MorDalPhos with [Pd(?-cinnamyl)Cl]2 enables the amination of electron-rich, electron-neutral, and electron-poor aryl phosphates with a board range of aromatic, aliphatic, and heterocyclic amines. Common functional groups such as ether, keto, ester, and nitrile show an excellent compatibility in this reaction condition. The solvent-free amination reactions are also successful in both solid coupling partners. The gram-scale cross-coupling is achieved by this catalytic system.
- Chen, Zicong,Chen, Xiangmeng,So, Chau Ming
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p. 6366 - 6376
(2019/05/24)
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- Oxalic amide ligands, and uses thereof in copper-catalyzed coupling reaction of aryl halides
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The present invention provides oxalic amide ligands and uses thereof in copper-catalyzed coupling reaction of aryl halides. Specifically, the present invention provides a use of a compound represented by formula I, wherein definitions of each group are described in the specification. The compound represented by formula I can be used as a ligand in copper-catalyzed coupling reaction of aryl halides for the formation of C—N, C—O and C—S bonds.
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Page/Page column 77-78
(2020/01/09)
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- ENOBIN axial chiral compound and synthesizing method thereof
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The invention belongs to the field of axial chiral compounds and discloses an ENOBIN axial chiral compound and a synthesizing method thereof. The general formula of the ENOBIN axial chiral compound isas shown in the specification, wherein Ar is as shown in the specification, each of R1 and R2 is independently selected from hydrogen, alkyl, alkynyl, alkenyl, phenyl, alkoxy, amino, halogen, trifluoromethyl, cyano, hydroxyl, aldehyde group, carboxyl, acetyl, ester group, nitro, amide group, sulfonyl, sulfonic acid group, sulfydryl and sulfanyl; R3 is selected from alkyl, phenyl and substituted phenyl; R4 is selected from hydrogen, alkyl, alkynyl, alkenyl, alkoxy, halogen, cyano, hydroxyl, aldehyde group, carboxyl and ester group; n is 0 or 1; R9 is alkoxy. The ENOBIN axial chiral compound and the synthesizing method thereof have the advantages that the novel-structure ENOBIN axial chiral compound is designed, and the ENOBIN axial chiral compound has a unique space structure and is the supplement of a BINOL and SPINOL framework; the ENOBIN framework is built by using chiral acid to catalyze the asymmetrical hydrogenation arylation of aryl alkyne, and good yield and excellent E/Z selectivity and enantioselectivity are achieved.
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Paragraph 0072
(2019/08/07)
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- Main-Group-Catalyzed Reductive Alkylation of Multiply Substituted Amines with Aldehydes Using H2
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Given the growing demand for green and sustainable chemical processes, the catalytic reductive alkylation of amines with main-group catalysts of low toxicity and molecular hydrogen as the reductant would be an ideal method to functionalize amines. However, such a process remains challenging. Herein, a novel reductive alkylation system using H2 is presented, which proceeds via a tandem reaction that involves the B(2,6-Cl2C6H3)(p-HC6F4)2-catalyzed formation of an imine and the subsequent hydrogenation of this imine catalyzed by a frustrated Lewis pair (FLP). This reductive alkylation reaction generates H2O as the sole byproduct and directly functionalizes amines that bear a remarkably wide range of substituents including carboxyl, hydroxyl, additional amino, primary amide, and primary sulfonamide groups. The synthesis of isoindolinones and aminophthalic anhydrides has also been achieved by a one-pot process that consists of a combination of the present reductive alkylation with an intramolecular amidation and intramolecular dehydration reactions, respectively. The reaction showed a zeroth-order and a first-order dependence on the concentration of an imine intermediate and B(2,6-Cl2C6H3)(p-HC6F4)2, respectively. In addition, the reaction progress was significantly affected by the concentration of H2. These results suggest a possible mechanism in which the heterolysis of H2 is facilitated by the FLP comprising THF and B(2,6-Cl2C6H3)(p-HC6F4)2.
- Hoshimoto, Yoichi,Kinoshita, Takuya,Hazra, Sunit,Ohashi, Masato,Ogoshi, Sensuke
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supporting information
p. 7292 - 7300
(2018/06/01)
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- Double C-S bond formation: Via C-H bond functionalization: Synthesis of benzothiazoles and naphtho[2,1- d] thiazoles from N -substituted arylamines and elemental sulfur
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A novel, atom economic, and environmentally friendly method for the synthesis of 2-substituted benzothiazoles and 2-substituted naphtho[2,1-d]thiazoles from N-substituted arylamines and elemental sulfur has been developed under metal-free conditions. The reaction underwent the process of double C-S bond formation through C-H bond functionalization.
- Zhu, Xiaoming,Yang, Yuzhong,Xiao, Genhua,Song, Jianxin,Liang, Yun,Deng, Guobo
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supporting information
p. 11917 - 11920
(2017/11/06)
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- Co(II) PCP Pincer Complexes as Catalysts for the Alkylation of Aromatic Amines with Primary Alcohols
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Efficient alkylations of amines by alcohols catalyzed by well-defined Co(II) complexes are described that are stabilized by a PCP ligand (N,N′-bis(diisopropylphosphino)-N,N′-dimethyl-1,3-diaminobenzene) based on the 1,3-diaminobenzene scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant nonprecious metal catalysts and is based on the acceptorless alcohol dehydrogenation concept. A range of primary alcohols and aromatic amines were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields.
- Mastalir, Matthias,Tomsu, Gerald,Pittenauer, Ernst,Allmaier, Günter,Kirchner, Karl
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supporting information
p. 3462 - 3465
(2016/07/26)
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- Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride MnIand FeIIPNP Pincer Complexes
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Herein, we describe an efficient coupling of alcohols and amines catalyzed by well-defined isoelectronic hydride MnIand FeIIcomplexes, which are stabilized by a PNP ligand based on the 2,6-diaminopyridine scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant non-precious metal catalysts, and is based on the acceptorless alcohol dehydrogenation concept. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted in good to excellent isolated yields. Although in the case of Mn selectively imines were obtained, with Fe—exclusively monoalkylated amines were formed. These reactions proceed under base-free conditions and required the addition of molecular sieves.
- Mastalir, Matthias,Glatz, Mathias,Gorgas, Nikolaus,St?ger, Berthold,Pittenauer, Ernst,Allmaier, Günter,Veiros, Luis F.,Kirchner, Karl
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supporting information
p. 12316 - 12320
(2016/08/24)
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- Alanine triazole iridium-catalyzed C–N bond formation through borrowing hydrogen strategy
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An efficient synthesis of secondary amines has been described through alanine triazole iridium-catalyzed C–N bond formation of an aromatic amine and an alkyl amine using the borrowing hydrogen strategy. In addition, it was observed that alanine triazole iridium is also an efficient catalyst to promote C–N bond formation of an aromatic amine and alcohols with good to excellent yields.
- Yu, Xiaoli,Zhao, Ranran,Wan, Huida,Yang, Yongchun,Wang, Dawei
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supporting information
p. 4588 - 4591
(2016/09/23)
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- A ruthenium-based catalytic system for a mild borrowing-hydrogen process
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The alkylation of arylamines using stoichiometric amounts of aliphatic and benzylic alcohols in the presence of tBuOK was carried out at 55 °C using a low catalyst loading of [Ru(cod)-Cl2]n/PTA (1,3,5-triaza-7-phosphaadamantane). The overall borrowing-hydrogen process does not require a controlled nitrogen atmosphere, and it could also be carried out at room temperature using higher loading of base. A wide range of substrates can be used in this transformation, and it has a good tolerance of different substituents. This catalytic system proved also to be efficient for other hydrogen-transfer reactions such as a tandem oxidation/C-C coupling between 1-phenylethanol and primary alcohols.
- Jumde, Varsha R.,Gonsalvi, Luca,Guerriero, Antonella,Peruzzini, Maurizio,Taddei, Maurizio
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p. 1829 - 1833
(2015/05/27)
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- Photocatalytic secondary amine synthesis from azobenzenes and alcohols on TiO2 loaded with Pd nanoparticles
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Photoirradiation (λ > 300 nm) of TiO2 loaded with Pd nanoparticles (ca. 2 wt%, 5 nm diameter) in water containing alcohols and azobenzene derivatives at room temperature successfully produces the corresponding secondary amines with high yields.
- Selvam, Kaliyamoorthy,Sakamoto, Hirokatsu,Shiraishi, Yasuhiro,Hirai, Takayuki
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p. 2856 - 2860
(2015/04/22)
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- Fe@Pd/C: An efficient magnetically separable catalyst for direct reductive amination of carbonyl compounds using environment friendly molecular hydrogen in aqueous reaction medium
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Direct reductive amination of carbonyl compounds with variety of amines has been reported by using magnetically separable Fe@Pd/C as an efficient catalyst in aqueous reaction medium. The developed methodology offers synthesis of various secondary and tertiary amines using different aldehydes and ketones with amines giving excellent yield. Moreover, the magnetically separable Fe@Pd/C catalyst was easily separated from reaction mixture and can be recycled for further reaction.
- Patil, Nilesh M.,Bhanage, Bhalchandra M.
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p. 182 - 189
(2015/03/30)
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- CuI/Oxalic Diamide Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amines
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A class of oxalic diamides are found to be effective ligands for promoting CuI-catalyzed aryl amination with less reactive (hetero)aryl chlorides. The reaction proceeds at 120 °C with K3PO4 as the base in DMSO to afford a wide range of (hetero)aryl amines in good to excellent yields. The bis(N-aryl) substituted oxalamides are superior ligands to N-aryl-N′-alkyl substituted or bis(N-alkyl) substituted oxalamides. Both the electronic nature and the steric property of the aromatic rings in ligands are important for their efficiency.
- Zhou, Wei,Fan, Mengyang,Yin, Junli,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 11942 - 11945
(2015/10/06)
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- Reductive N-alkylation of nitro compounds to N -Alkyl and N, N -dialkyl amines with glycerol as the hydrogen source
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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.
- Cui, Xinjiang,Deng, Youquan,Shi, Feng
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p. 808 - 811
(2013/06/27)
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- CuI/DMPAO-catalyzed N-arylation of acyclic secondary amines
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DMPAO has been found to be a powerful ligand to enable copper-catalyzed coupling of aryl halides with aliphatic acyclic secondary amines take place under relatively mild conditions, and coupling of aryl halides with primary amines and cyclic secondary amines proceeds at low catalyst loading.
- Zhang, Yu,Yang, Xinye,Yao, Qizheng,Ma, Dawei
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supporting information; experimental part
p. 3056 - 3059
(2012/07/28)
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- Organic ligand-free alkylation of amines, carboxamides, sulfonamides, and ketones by using alcohols catalyzed by heterogeneous Ag/Mo oxides
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Complicated and expensive organic ligands are normally essential in fine chemical synthesis at preparative or industrial levels. The synthesis of fine chemicals by using heterogeneous catalyst systems without additive organic ligand is highly desirable but severely limited due to their poor generality and rigorous reaction conditions. Here, we show the results of carbon-nitrogen or carbon-carbon bond formation catalyzed by an Ag/Mo hybrid material with specific Ag6Mo10O33 crystal structure. 48 nitrogen- or oxygen-containing compounds, that is, amines, carboxamides, sulfonamides, and ketones, were successfully synthesized through a borrowing-hydrogen mechanism. Up to 99% isolated yields were obtained under relatively mild conditions without additive organic ligand. The catalytic process shows promise for the efficient and economic synthesis of amine, carboxamide, sulfonamide, and ketone derivatives because of the simplicity of the system and ease of operation. Copyright
- Cui, Xinjiang,Zhang, Yan,Shi, Feng,Deng, Youquan
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supporting information; experimental part
p. 1021 - 1028
(2011/03/20)
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- Ruthenium-catalyzed nitro and nitrile compounds coupling with alcohols: Alternative route for N-substituted amine synthesis
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The one-pot synthesis of N-substituted secondary amines from nitrobenzenes and benzonitriles has been developed (see scheme). This report presents a versatile and simple method for the synthesis of N-substituted amines in excellent yield and high efficiency from nitro and nitrile compounds with alcohols.
- Cui, Xinjiang,Zhang, Yan,Shi, Feng,Deng, Youquan
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supporting information; experimental part
p. 2587 - 2591
(2011/04/12)
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- Steric effects in palladium-catalysed amination of aryl triflates and nonaflates with the primary amines PhCH(R)NH2 (R=H, Me)
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A systematic study of the effects of aryl triflate and nonaflate structure on the yield of amination with the primary amines PhCH(R)NH2 (R=H, Me) under palladium catalysis has been carried out. High throughput screening indicated that a catalyst composed of X-Phos/Pd2(dba)3/1,4-dioxane was optimal based on a model reaction of Ar(ORf) [Rf=Tf (SO2CF3), Nf (SO2(CF2)3CF3)] with PhCH2NH2. Comparisons of the reactivity of various ArOTf and ArONf [Ar=4-MePh, 2-naphthyl, 1-naphthyl, 2-PhC6H4] indicated that both ortho substitution in the aryl electrophile and at the α-position on the amine are detrimental to the coupling particularly when they occur in combination. Despite being formally a monodentate ligand use of X-Phos leads to only small degrees of racemisation when using (R)-PhCH(Me)NH2 (typically resulting in a reduction from 97 to 86-94% ee for the amine stereocentre).
- Meadows, Rebecca E.,Woodward, Simon
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p. 1218 - 1224
(2008/09/18)
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- β-oxoacids esters in the synthesis of benzo[f]quinoline derivatives
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Condensation of ethyl acetoacetate and ethyl 3-oxo-3-(2-furyl-, 2-quinolyl-, 3-pyridyl)propanoates with azomethines of 2-naphthylamine series led to the formation of ethyl (3-arylbenzo[f]quinol-1-yl)acetates and of esters of the corresponding 3-aryl-1-heteryl-2-benzo[f]quinolylcarboxylic acids. The intermediate reaction products were isolated: ethyl 5-(2-naphthylamino)-3-oxo-5- phenylpentanoate, 2-[(aryl)(2-naphthylamino)methyl]-3-heteryl-3-oxopropanoates, dihydro and tetrahydro derivatives of benzoquinolylacetic and benzoquinolinecarboxylic acids. Nauka/Interperiodica 2007.
- Gusak,Kozlov
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p. 706 - 718
(2008/02/08)
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- Synthesis of benzo[f]quinoline derivatives by condensation of arylmethylene-2-naphthylamines with ethyl acetoacetate
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Reaction of arylmethylene-2-naphthylamines with ethyl acetoacetate affords ethyl (3-arylbenzo-[f]quinol-1-yl)acetates. On boiling thereof with ethanol solutions of alkali arise the corresponding salts that when treated with mineral acids undergo decarboxylation to yield 3-aryl-1-methylbenzo[f]quinolines. Heating of ethyl (3-arylbenzo[f]quinol-1-yl)acetates with dimethyl sulfate gives rise to 3-aryl-4-methyl-1-ethoxycarbonylmethylbenzo[f]quinolinium methylsulfates which afford the corresponding perchlorates after treatment with HClO4.
- Kozlov,Sauts,Gusak
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p. 531 - 538
(2007/10/03)
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- ONE-POT CHEMOSELECTIVE REDUCTIVE ALKYLATION OF NITROARENES: A NEW GENERAL METHOD OF SYNTHESIS OF ALKYLANILINES.
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A New facile and general synthesis of alkylanilines by one-pot reductive alkylation of nitroarenes is reported.This method is based on the "in situ" reduction by hydrides (LiAlH4 or NaBH4) in the presence of catalytic amounts of Pd/C, of nitronate adducts arising from the conjugate addition of Grignard reagents to mononitroarenes.LiAlH4 showed to be a more efficient but less selective reducing agent than NaBH4.The reaction can be successfully applied to mono, homo and hetero bicyclic systems and allows to introduce a large variety of alkyl chains without isomerisation phenomena.
- Bartoli, Giuseppe,Bosco, Marcella,Pozzo, Renato Dal,Petrini, Marino
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p. 4221 - 4226
(2007/10/02)
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- Reduction of Imines Using NADH Models
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Reduction of substituted N-arylideneanilines (3) and NN'-bisarylidene-ethylenediamines (10) in glacial acetic acid takes place smoothly with 3,5-bis(eyhoxycarbonyl)-2,6-dimethyl-1,4-dihydropyridine (Hantzsch ester) (2) at room temperature in the dark.One-pot reductive amination of aromatic aldehydes in glacial acetic acid using (2) was equally efficient.Enamines (6)-(8) underwent reduction on protonation with trifluoroacetic acid in dichloromethane, but not in acetic acid.These reductions are analogous to NADH-mediated biochemical reductive aminations of carbonyl compounds.Imines (3) are also reduced to the corresponding amines (4) when irradiated with Pyrex-filtered light in the presence of (2) in benzene under nitrogen.This photoreduction also proceeds in the solid state and a two-phase system was successfully tested for recycling an NADH model for photoreduction of (3) using sunlight.
- Singh, Serjinder,Sharma, Vijay K.,Gill, Sarbjeet,Sahota, Ravjit Inder K.
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p. 437 - 440
(2007/10/02)
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