- Copper-Catalyzed Intramolecular Amination of C(sp3)-H Bond of Secondary Amines to Access Azacycles
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The cross-coupling of C-N bond directly from inert C-H bonds is an ideal approach to synthesize saturated azacycles due to its high efficiency and atom economy. In this article, a copper-catalyzed intramolecular amination via the cross coupling of C(sp3)-H and N-H bonds of secondary amine has been reported, which exhibit excellent chemo- and regioselectivity, extensive substrate scope, and functional group tolerance in good to excellent yield, offering an efficient pathway to build nitrogen-containing heterocycle skeletons.
- Jin, Ruo-Xing,Dai, Jing-Cheng,Li, Yan,Wang, Xi-Sheng
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supporting information
p. 421 - 426
(2021/01/26)
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- Metal-free regioselective C-H amination for the synthesis of pyrazole-containing 2H-indazoles
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A general and practical regioselective approach for the C-H amination of 2H-indazoles under transition-metal-free conditions was developed. A series of substrates were tested showing eminent functional group tolerance and affording the C-N functionalization products in good to excellent yields. Mechanism studies revealed that a radical process was involved in this transformation.
- Wang, Kai,Wei, Tingting,Zhang, Yujia,Hou, Jiahao,Bai, Renren,Xie, Yuanyuan
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p. 1787 - 1794
(2021/03/14)
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- Sulfated polyborate: A dual catalyst for the reductive amination of aldehydes and ketones by NaBH4
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An efficient, quick, and environment-friendly one-pot reductive amination of aldehydes or ketones was developed. In ethanol at 70 °C, a imination catalyzed by sulfated polyborate and further reduced by sodium borohydride yields various amines. The present method has many significant benefits, including a shorter reaction time, excellent yields, and a hassle-free, straightforward experimental process. The reaction has a wide range of applications due to its flexibility, including secondary amine for reductive amination.
- Ganwir, Prerna,Chaturbhuj, Ganesh
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supporting information
(2021/05/19)
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- Rhodium catalyzed multicomponent dehydrogenative annulation: one-step construction of isoindole derivatives
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A strategy for one-pot synthesis of isoindoles is describedviaa catalytic multicomponent dehydrogenative annulation of diarylimines, vinyl ketones and simple amines. In the presence of a rhodium catalyst and Cu oxidant, four C-H and two N-H bonds are activated along with the formation of one new C-C and two new C-N bonds, leading to a series of isoindole derivatives in good to very high isolated yields.
- Cheng, Biao,Lyu, Hairong,Quan, Yangjian,Xie, Zuowei
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supporting information
p. 7930 - 7933
(2021/08/17)
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- Photocatalytic one-pot multidirectional N-alkylation over Pt/D-TiO2/Ti3C2: Ti3C2-based short-range directional charge transmission
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Visible-light-induced one-pot, multistep, and chemoselectivity adjustable reactions highlight the economical, sustainable, and green process. Herein, we report Pt nanoparticles dispersed on S and N co-doped titanium dioxide/titanium carbide (MXene) (3%Pt/
- Jiang, Heyan,Sheng, Meilin,Li, Yue,Kong, Shuzhen,Bian, Fengxia
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- Redox-Neutral Imination of Alcohol with Azide: A Sustainable Alternative to the Staudinger/Aza-Wittig Reaction
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The traditional Staudinger/aza-Wittig reaction represents one of the most powerful tools for imine formation. However, for this multistep procedure, the sacrificial phosphine has to be used, resulting in difficulties in the purification process and waste disposal at the same time. Here, we report a redox-neutral azide-alcohol imination methodology enabled by a base-metal nickel PN3 pincer catalyst. The one-step, waste-free, and high atom-economical features highlight its advantages further. Moreover, mechanistic insight suggests a non-metal-ligand cooperation pathway based on the observation of an intermediate and density functional theory calculations.
- Li, Huaifeng,Lupp, Daniel,Das, Pradip K.,Yang, Li,Gon?alves, Théo P.,Huang, Mei-Hui,El Hajoui, Marwa,Liang, Lan-Chang,Huang, Kuo-Wei
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p. 4071 - 4076
(2021/04/12)
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- Direct synthesis of imines from nitro compounds and biomass-derived carbonyl compounds over nitrogen-doped carbon material supported Ni nanoparticles
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The selective synthesis of imines from biomass-derived chemicals over heterogeneous non-noble metal catalysts is of great importance for organic transformation. Herein, non-noble heterogeneous nitrogen-doped carbon supported Ni catalysts (abbreviated as Ni/CN-MgO-T, whereTrepresents the pyrolysis temperature) have been facilely prepared from the simple pyrolysis of Ni precursors and biomass, and Ni/CN-MgO-600 with the smallest size of Ni nanoparticles demonstrated the highest catalytic activity. The reductive coupling of nitroarenes and carbonyl compounds could be performed under mild conditions (80 °C, and 10 bar H2), affording structurally-diverse imines with high to excellent yields (84.2-98.1%). Thanks to the mild reaction conditions, the developed method showed good tolerance to other functional groups such as nitriles, halogen and vinyl groups.
- Li, Bo,Wang, Yanxin,Chi, Quan,Yuan, Ziliang,Liu, Bing,Zhang, Zehui
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p. 4464 - 4471
(2021/03/15)
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- Tandem imine formationviaauto-hydrogen transfer from alcohols to nitro compounds catalyzed by a nanomagnetically recyclable copper catalyst under solvent-free conditions
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A direct imination reaction was developed by tandem reaction of alcohols and nitro compounds in the presence of Cu-isatin Schiff base-γ-Fe2O3as a nanomagnetically recyclable catalyst under solvent-free conditions. By this method, various imines were prepared in good to high yields from one-pot reaction of various alcohols (primary aromatic and aliphatic) and nitro compounds (aromatic and aliphatic)viaan auto-hydrogen transfer reaction. Use of an inexpensive and easily reusable catalyst, without requiring any additives or excess amounts of benzyl alcohol as the reaction solvent are the other advantages of this method. This catalytic system has the merits of cost effectiveness, environmental benignity, excellent recyclability and good reproducibility.
- Derakhshan, Seyed Ruhollah,Hosseini Moghadam, Hadis,Sansano, José Miguel,Sobhani, Sara
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p. 19121 - 19127
(2021/06/03)
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- Iron-Catalyzed Hydrogen Transfer Reduction of Nitroarenes with Alcohols: Synthesis of Imines and Aza Heterocycles
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A straightforward and selective reduction of nitroarenes with various alcohols was efficiently developed using an iron catalyst via a hydrogen transfer methodology. This protocol led specifically to imines in 30-91% yields, with a good functional group tolerance. Noticeably, starting from o-nitroaniline derivatives, in the presence of alcohols, benzimidazoles can be obtained in 64-72% yields when the reaction was performed with an additional oxidant, DDQ, and quinoxalines were prepared from 1,2-diols in 28-96% yields. This methodology, unprecedented at iron for imines, also provides a sustainable alternative for the preparation of quinoxalines and benzimidazoles.
- Wu, Jiajun,Darcel, Christophe
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p. 1023 - 1036
(2021/01/09)
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- Efficient Imine Formation by Oxidative Coupling at Low Temperature Catalyzed by High-Surface-Area Mesoporous CeO2 with Exceptional Redox Property
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High-surface-area mesoporous CeO2 (hsmCeO2) was prepared by a facile organic-template-induced homogeneous precipitation process and showed excellent catalytic activity in imine synthesis in the absence of base from primary alcohols and amines in air atmosphere at low temperature. For comparison, ordinary CeO2 and hsmCeO2 after different thermal treatments were also investigated. XRD, N2 physisorption, UV-Raman, H2 temperature-programmed reduction, O2 temperature-programmed desorption, EPR spectroscopy, and X-ray photoelectron spectroscopy were used to unravel the structural and redox properties. The hsmCeO2 calcined at 400 °C shows the highest specific surface area (158 m2 g?1), the highest fraction of surface coordinatively unsaturated Ce3+ ions (18.2 %), and the highest concentration of reactive oxygen vacancies (2.4×1015 spins g?1). In the model reaction of oxidative coupling of benzyl alcohol and aniline, such an exceptional redox property of the hsmCeO2 catalyst can boost benzylideneaniline formation (2.75 and 5.55 mmol (Formula presented.) h?1 based on >99 % yield at 60 and 80 °C, respectively) in air with no base additives. It can also work effectively at a temperature of 30 °C and in gram-scale synthesis. These are among the best results for all benchmark ceria catalysts in the literature. Moreover, the hsmCeO2 catalyst shows a wide scope towards primary alcohols and amines with good to excellent yield of imines. The influence of reaction parameters, the reusability of the catalyst, and the reaction mechanism were investigated.
- Wu, Shipeng,Wang, Yinghao,Cao, Qiue,Zhao, Qihua,Fang, Wenhao
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supporting information
p. 3019 - 3028
(2020/12/11)
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- Highly efficient and selective one-pot tandem imine synthesis via amine-alcohol cross-coupling reaction catalysed by chromium-based MIL-101 supported Au nanoparticles
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One-pot tandem synthesis of imines from alcohols and amines is regarded as an effective, economic and green approach under mild conditions. In this work, Au nanoparticles (NPs) dispersed on MIL-101 (Au/MIL-101) were demonstrated as highly active and selective bifunctional heterogeneous catalyst for production of various imine derivatives with excellent yields, via amine-alcohol cross-coupling reaction at 343 K in an open flask under an Ar atmosphere. Various physicochemical techniques, including inductively coupled plasma optical emission spectroscopy (ICP-OES), powder X-ray diffraction (P-XRD), X-ray photoelectron spectroscopy (XPS) transmission electron microscopy (TEM) and N2 adsorption-desorption, were used to characterize of the Au/MIL-101 catalyst. The obtained bifunctional catalyst is highly active and selective towards one-pot imine formation and exhibited the highest TOF (30.15-51.47 h?1) among all the ever-reported MOF-supported Au catalysts. The reaction mechanism of the imine formation from alcohol and amine over Au/MIL-101 catalyst was proposed. Mechanism experiment results demonstrate that Au NPs highly effective in activating oxidation of benzyl alcohol to benzaldehyde while the Lewis acid sites on MIL-101 catalyzed the second condensation step without interfering with the oxidation step. As a result, the excellent catalytic performance of Au/MIL-101 can be ascribed to the synergistic effect between Au NPs with Lewis acid sites in MIL-101.
- Gülcan, Mehmet,Gumus, Ilkay,Karatas, Yasar,Ruzgar, Adem
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- Functional POM-catalyst for selective oxidative dehydrogenative couplings under aerobic conditions
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Development of selective and efficient reusable catalytic systems for sustainable chemical production under benign conditions is attractive and received much attention. Herein, we report a rod-shaped octadecyl trimethylammonium functionalized Keggin-type polyoxometalate [PMO12O40] hybrids (OTA-POM) as an efficient heterogeneous catalyst for selective oxidative dehydrogenative couplings under aerobic conditions without any additive or external base. The catalyst recovery and subsequent five successive recyclability studies of hybrid POM confirms the heterogeneous nature of present catalytic system.
- Samaraj, Elavarasan,Balaraman, Ekambaram,Manickam, Sasidharan
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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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- Efficient imine synthesisviaoxidative coupling of alcohols with amines in an air atmosphere using a mesoporous manganese-zirconium solid solution catalyst
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Direct oxidative coupling of alcohols with amines using a non-precious metal oxide catalyst under mild conditions is highly desirable for imine synthesis. In this work, a mesoporous Mn1ZrxOysolid solution catalyst prepared by a co-precipitation method showed excellent catalytic performance in imine synthesis from primary alcohols and amines without base additives in an air atmosphere. XRD, N2physisorption, H2-TPR, O2-TPD, EPR and XPS were comprehensively used to unravel its structural, redox and amphoteric properties that closely depended on the interaction between MnOyand ZrO2with a variable Zr ratio. The Mn1Zr0.5Oycatalyst presented the highest fractions of Mn3+ions and reactive oxygen species on the surface, and the highest concentrations of acidic-basic sites, which were disclosed to play important roles in activating alcohols and molecular O2in the rate-determining step. In the model reaction of oxidative coupling of benzyl alcohol with aniline, such enhanced features of the Mn1Zr0.5Oycatalyst can promote the intrinsic catalytic activity (iTOF of 1.87 h?1) and boost benzylideneaniline formation (5.56 mmol gcat.?1h?1) based on a >99% yield at 80 °C respectively at a fast response. It can also work effectively at a room temperature of 30 °C, as well as for the gram-grade synthesis. This is one of the best results among all the MnOy-based catalysts in the literature. Moreover, this catalyst showed good stability and a wide substrate scope with good to excellent yields of imines.
- Wu, Shipeng,Zhang, Hao,Cao, Qiue,Zhao, Qihua,Fang, Wenhao
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p. 810 - 822
(2021/02/26)
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- Dehydrogenation and α-functionalization of secondary amines by visible-light-mediated catalysis
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A visible-light-mediated process for dehydrogenation of amines has been described. The given protocol showed a broad substrate scope, mild reaction conditions and excellent results without the requirement of tedious purification. This process can be applied in one-pot functionalization of secondary amines with various nucleophiles through the cooperation of visible-light and Lewis acid catalysis, leading to the structurally varied essential components of biologically active molecules. In addition, Stern-Volmer studies and quenching experiments revealed the role of a catalyst and led to the proposed mechanism of this transformation.
- Bujok, Robert,Morawska, Paulina,Pawlowski, Robert,Stanek, Filip,Stodulski, Maciej
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supporting information
p. 2103 - 2112
(2020/03/27)
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- Cross dehydrogenative coupling strategy for allylation of benzylanilines promoted by DDQ
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A cross dehydrogenative coupling strategy for allylation of benzylanilines promoted by DDQ is reported, which uses nonmetallic quinone DDQ as an oxidant in the allylation of N-benzylanilines under mild conditions. C–C bond with high selectivity and activity was constructed in this reaction and homoallylic amines were obtained with yields of up to 99%.
- Xiong, Ruimei,Hussain, Muhammad Ijaz,Liu, Qing,Xia, Wen,Xiong, Yan
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supporting information
(2019/12/11)
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- Tert-Butyl Hydroperoxide-Mediated Oxo-Sulfonylation of 2 H-Indazoles with Sulfinic Acid toward Indazol-3(2 H)-ones
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A new and efficient oxo-sulfonylation protocol has been established for the synthesis of N-sulfonylated indazolones employing sulfinic acid as a sulfonylating agent using tert-butyl hydroperoxide (TBHP) under ambient air. A series of structurally diverse 1-sulfonylindazol-3(2H)-one derivatives were obtained in good yields. A radical reaction mechanism has been proposed for this transformation.
- Ghosh, Payel,Mondal, Susmita,Hajra, Alakananda
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supporting information
p. 1086 - 1090
(2020/02/04)
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- Retraction: Harnessing Thiol as a Benzyl Reagent for Photocatalytic Reductive Benzylation of Imines (Organic Letters DOI: 10.1021/2Facs.orglett.0c00065)
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The authors retract this article after finding in subsequent studies that the quality of the purchased catalysts has a notable impact on the reproducibility of the results. Accordingly, the authors note that additional work is necessary to understand the
- Zhang, Jinghui,Zhang, Muliang
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supporting information
p. 2112 - 2112
(2020/02/15)
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- Study on the interaction of triaryl-dihydro-1,2,4-oxadiazoles with α-glucosidase
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Purpose: One of the therapeutic approaches in the management of Type 2 diabetes is delaying the absorption of glucose through α-glucosidase enzymes inhibition, which can reduce the incidence of postprandial hyperglycemia. The existence of chronic postpran
- Khosravi, Arefeh,Vaezi, Gholamhassan,Hojati, Vida,Abdi, Khosrou
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p. 109 - 117
(2020/01/11)
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- Diethylsilane as a Powerful Reagent in Au Nanoparticle-Catalyzed Reductive Transformations
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Diethylsilane (Et2SiH2), a simple and readily available dihydrosilane, that exhibits superior reactivity, as compared to monohydrosilanes, in a series of reductive transformations catalyzed by recyclable and reusable Au nanoparticles (1 mol-%) supported on TiO2. It reduces aldehydes or ketones almost instantaneously at ambient conditions. It can be used in a one pot rapid reductive amination procedure, in which premixing of aldehyde and amine is required prior to the addition of the reducing agent and the catalyst, even in a protic solvent. An unprecedented method for the synthesis of N-arylisoindolines is also shown in the reductive amination between o-phthalaldehyde and anilines. In this transformation, it is proposed that the intermediate N,2-diphenylisoindolin-1-imines are reduced stepwise to the isoindolines. Finally, Et2SiH2 readily reduces amides into amines in excellent yields and shorter reaction times relative to previously known analogous nano Au(0)-catalyzed protocols.
- Louka, Anastasia,Kidonakis, Marios,Saridakis, Iakovos,Zantioti-Chatzouda, Elisavet-Maria,Stratakis, Manolis
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p. 3508 - 3514
(2020/06/02)
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- Catalyst- And solvent-free efficient access to: N -alkylated amines via reductive amination using HBpin
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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
- Bauri, Somnath,Pandey, Vipin K.,Rit, Arnab
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supporting information
p. 3853 - 3857
(2020/07/27)
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- Kinetic and thermodynamic modulation of dynamic imine libraries driven by the hexameric resorcinarene capsule
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The composition of dynamic covalent imine libraries (DCL) adapts to the presence of the hexameric resorcinarene capsule. In the presence of the self-assembled capsule, a kinetic and thermodynamic modulation of the imine constituents of the DCLs was observed, which was induced by an unusual predatory action of the capsule on specific imine constituents. More complex 2 × 2 DCLs also adapt to the presence of the hexameric capsule, showing a thermodynamic and kinetic modulation of the constituents induced by the predatory action of the capsule. By cross-referencing experimental data, a good selectivity (up to 66%) for one constituent can be induced in a 2 × 2 DCL.
- Gambaro, Stefania,Talotta, Carmen,Della Sala, Paolo,Soriente, Annunziata,De Rosa, Margherita,Gaeta, Carmine,Neri, Placido
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supporting information
p. 14914 - 14923
(2020/10/13)
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- Study of the versatility of CuBTC?IL-derived materials for heterogeneous catalysis
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The versatility of CuBTC (or HKUST-1) MOF materials to be functionalized to tune their catalytic activity performance was evaluated. The MOFs were functionalized with ionic liquids (ILs) to give rise to catalysts able to adsorb CO2and react with epoxides to produce carbonates. The materials are active for this reaction and show good conversion rates at 100 °C and 7 bar CO2, confirming their ability to fix this gas and transform it into valuable products. In addition, the MOF?IL composite material1can be functionalized to give rise to a bimetallic catalyst, taking advantage of the N-heterocyclic carbene present in the imidazolium-based ILs. Therefore, the material was reacted with palladium dichloride, yielding CuBTC?IL-(NHC)Pd (1Pd) which has been tested for homocoupling of alkynes and imination of benzyl alcohol reactions. The recyclability of the catalysts has been studied and hot filtration tests have been made.
- Arriortua, Maria I.,Fernández de Luis, Roberto,Fidalgo-Marijuan, Arkaitz,Iglesias, Marta,Larrea, Edurne S.,Maya, Eva M.
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p. 2904 - 2913
(2020/05/18)
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- Rational Design of Cobalt-Platinum Alloy Decorated Cobalt Nanoparticles for One-Pot Synthesis of Imines from Nitroarenes and Aldehydes
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Developing high-performance heterogeneous catalysts for one-pot reductive amination reactions is critically important for pharmaceutical and agrochemical synthetic industries. In this work, N-doped carbon nanotubes supported CoPt alloy decorated Co nanoparticles (NPs) are successfully fabricated. As a consequence, the resultant catalyst exhibits desirable activity, selectivity and stability toward the one-pot synthesis of imines. More importantly, the extensive experimental studies and density function theory (DFT) calculations results reveal that the high catalytic activity of the catalyst is mainly due to the co-existence of CoPt alloy NPs and Co NPs with Co?Nx active sites. The high selectivity of imines could be ascribed to the following aspects: (1) competitively preferred adsorption of nitroarenes to avoid side-hydrogenation of aldehydes; (2) weakened adsorption of imines to minimize its over-hydrogenation. This work may provide a promising direction and strategy to design high-performance reductive amination catalysts for industrial applications.
- Gong, Wanbing,Han, Miaomiao,Chen, Chun,Lin, Yue,Wang, Guozhong,Zhang, Haimin,Zhao, Huijun
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p. 5948 - 5958
(2020/10/02)
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- Highly efficient microwave assisted synthesis of magnetically separable GO-CoFe2O4 nanocomposite for visible light induced oxidative coupling of benzyl amines
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The present paper describes an efficient microwave-assisted synthesis of magnetic CoFe2O4 and its nanocomposite with graphene oxide (GO-CoFe2O4) for photocatalytic oxidative coupling of benzylamines to the corresponding imines using molecular oxygen. The surface morphologies and structures of both CoFe2O4 and GO-CoFe2O4 nanocomposites were investigated by various spectroscopic techniques including powder X-ray diffraction (XRD), Transmission electron microscopy (HR-TEM), Fourier transform infrared spectroscopy (FTIR), nitrogen adsorption–desorption isotherms, X-ray photoelectron spectroscopy (XPS) and Raman Spectroscopy. Photocatalytic oxidative coupling experiments demonstrated that GO-CoFe2O4 exhibited significantly higher efficiency than CoFe2O4 nanoparticles, suggesting that GO played an important role in the reaction. Moreover, the magnetic nature of the synthesized nanocomposite provided facile recovery of the material by the influence of an external magnet.
- Jain, Suman L.,Khatri, Praveen K.,Sadanandan, Aathira M.
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- Method for synthesizing aluminum phosphate molecular sieve catalytic imine
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The invention discloses a method for catalyzing synthesis of an imine by using an aluminum phosphate molecular sieve, and belongs to the technical field of catalytic synthesis of imines. Under the action of an HP-MeAlPO-5 molecular sieve, air or oxygen is used as an oxidant, and an amine and an alcohol which contain different substituents are directly subjected to oxidative coupling to synthesizethe imine under mild conditions. According to the method provided by the invention, the reaction conditions of the adopted catalytic system are mild, and the TOF is high; a reaction can efficiently catalyze the synthesis of the imine at room temperature under air; and the method can adopt transition metals, which are cheap and easy to obtain, such as iron, cobalt and nickel as a molecular sieve dopant, and the availability of the molecular sieve is improved.
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Paragraph 0056-0058
(2020/06/02)
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- Method for synthesizing imine by catalyzing alcohol-amine through NNN cobalt complex
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The invention discloses a method for synthesizing imine by catalyzing alcohol-amine through an NNN cobalt complex. The method comprises the following steps: in a nitrogen atmosphere and at the temperature of 75-85 DEG C, taking an organic solvent as a solvent, taking an NNN cobalt complex (LCoCl2) as a catalyst under an alkaline condition, and reacting arylamine with aryl methanol for 40-55 hoursto obtain imine. The preparation method has the characteristics of high yield, few by-products, environmental friendliness and the like and has a wide application prospect.
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Paragraph 0042-0045
(2020/07/02)
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- Silver nanoparticles stabilized by a metal-organic framework (MIL-101(Cr)) as an efficient catalyst for imine production from the dehydrogenative coupling of alcohols and amines
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In this paper, we present silver nanoparticles supported on a metal-organic framework (Ag@MIL-101) as a catalyst for the one-pot tandem synthesis of imines from alcohols and amines. The Ag@MIL-101 catalyst was fabricated using the liquid phase impregnation technique as an easy and effective method. The morphology and chemical structure of the prepared catalyst were systemically evaluated by inductively coupled plasma optical emission spectroscopy (ICP-OES), powder X-ray diffraction (P-XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The highly crystalline feature of the Ag metal nanoparticles on bifunctional MIL-101(Cr) was revealed by TEM and HRTEM analyses. The Ag@MIL-101 catalyst was examined as a catalyst for the synthesis of different imine derivatives. The catalytic performance of the Ag@MIL-101 catalyst was monitored by GC-MS and 1H-NMR analyses for the dehydrogenative coupling of alcohols and amines. Furthermore, the effect of various factors such as the amount of catalyst, base, temperature and solvent was investigated to optimize the conditions for the best performance of the Ag@MIL-101 catalyst. Catalytic activity test results showed that the Ag@MIL-101 catalyst has a good catalytic activity with TOF values in the range of 12.7-14.6 h-1 in the synthesis of various imines.
- Gumus, Ilkay,Karata?, Yas?r,Gülcan, Mehmet
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p. 4990 - 4999
(2020/11/02)
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- Thermally regulated molybdate-based ionic liquids toward molecular oxygen activation for one-pot oxidative cascade catalysis
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One-pot oxidative cascade catalysis plays a central role in the synthesis of key pharmaceutical and industrial molecules. Although ionic liquids are one of the most promising solvents and reaction media, the breakthrough of their catalysis in aerobic oxidation is very challenging due to the difficulty in the direct activation of molecular oxygen. Herein, a family of novel thermally regulated molybdate-based ionic liquids (Mo-ILs) has been designed and developed for the first time toward molecular oxygen activation for highly efficient tandem oxidative catalysis. Three diverse one-pot oxidative cascade processes for the syntheses of various flavones, imines, and benzyl benzoates were achieved with good to excellent yields using the Mo-IL [Bmim]2[MoO4] as a catalyst under air conditions. The results of spectroscopic investigations and quantum-chemical calculations further demonstrated that a thermally regulated proton migration between the cation [Bmim] and anion [MoO4] was the key to forming N-heterocyclic carbene and thereby to effortlessly promoting the generation of O2- active species from molecular oxygen, which results in excellent catalytic performance in these three aerobic tandem oxidations. Our work extends the application area of ILs as the sole catalyst to one-pot aerobic oxidative cascade catalysis, which could have pronounced implications in future work.
- Song, Zhibin,Huang, Wei,Zhou, Yan,Tian, Zi-Qi,Li, Zhang-Min,Tao, Duan-Jian
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supporting information
p. 103 - 109
(2020/01/21)
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- Ultrasound-assisted construction of a Z-scheme heterojunction with g-C3N4 nanosheets and flower-like Bi2WO6 microspheres and the photocatalytic activity in the coupling reaction between alcohols and amines under visible light irradiation
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Flower-like Bi2WO6 microspheres and bulk g-C3N4 were prepared by the hydrothermal method and high-temperature calcining method, respectively. A new method based on the combination of ultrasonic stripping and mechanical stirring was used to obtain uniform composite x-Bi2WO6/g-C3N4 (x is the Bi2WO6 mass ratio) photocatalysts with a Z-scheme heterojunction. In the reaction of benzyl alcohol and aniline to form imine, the optimal composite, 30percent-Bi2WO6/g-C3N4, showed a conversion rate of 87.6percent, which is much higher than that of pure Bi2WO6 and g-C3N4. Characterization by SEM and TEM showed that the ultrasonically stripped g-C3N4 significantly reduced the radial dimension compared to bulk g-C3N4. A uniformly dispersed photocatalytic material was formed, and it maintained a flower-like microsphere structure. Materials characterized by N2 adsorption–desorption isotherms (BET) showed that the specific surface area of the g-C3N4 nanosheets increased by approximately ten times after ultrasonic stripping. The photostability of the composite was verified by cyclic experiments. Under visible light irradiation, the activation energy of the coupling reaction between benzyl alcohol and aniline was found to be decreased by 29.8 kJ mol?1. A capture experiment was used to verify the active species in the photocatalytic system, with the reaction found to be mainly completed through the synergistic action of h+, e? and ?O2?.
- Hao, Xueli,Li, Enbo,Li, Haiying,Li, Jingyi,Wang, Yan,Wang, Zhibao,Yu, Xiujuan,Zhang, Zhiying
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- Insight into Ce Doping Induced Oxygen Vacancies over Ce-Doped Mno2 Catalysts for Imine Synthesis
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The pursuit of modern sustainable chemistry has stimulated the development of innovative catalytic processes that enable chemical transformations to be performed under mild and clean conditions with high efficiency. Here, an amorphous sheet-like MnO2 (Ce-doped MnO2: CMBO) was obtained after Ce doping, which exhibits excellent catalytic performance for the oxidation coupling of alcohol and aniline. Conversion of 99% and a selectivity of 99% could be achieved within 6 h at 60 oC under air atmosphere, and the formation rate of target product was up to 30.2 μmol·h–1·m–2. Based on a series of characterizations, it was found that the doping of Ce into the MnO2 could increase the concentration of the oxygen vacancies, thus forming abundant active surface oxygen species and favoring the mobility of lattice oxygen, which are the main reasons for the greatly enhanced catalytic performance of CMBO. This work indicates that increasing oxygen vacancy by element doping may serve as a facile and efficient way to enhance catalytic performance of transition metal oxide.
- Shen, Haidong,Bu, Jun,Wang, Wenbin,Wu, Chen,Cao, Yueling,Zhang, Baoliang,Zhang, Qiuyu,Zhang, Hepeng
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supporting information
p. 1353 - 1359
(2020/08/25)
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- Tuning effect of amorphous Fe2O3on Mn3O4for efficient atom-economic synthesis of imines at low temperature: Improving [O] transfer cycle of Mn3+/Mn2+in Mn3O4
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A facile and scaled-up synthesis route to efficient and environment-friendly metal oxide catalysts with desirable properties is of great practical importance, owing to their excellent performance as heterogeneous catalysts in organic synthesis. Herein, a novel amorphous Fe2O3 modified Mn3O4 catalyst (Fe5Mn5-100) has been prepared by adopting a simple co-precipitation method following low temperature baking. Fe5Mn5-100 showed exceptionally high catalytic activity for the atom-economic production of imine from benzyl alcohol with aniline, giving a 98% imine yield at 60 °C in only 3 h, which is higher than all of the reported non-noble and noble metal catalysts. Importantly, Fe5Mn5-100 could still exhibit extraordinary catalytic performance on a large-scale reaction without any solvent, including the frequently used toxic mesitylene, xylene or toluene. Interestingly, the amorphous Fe2O3-100 provided no catalytic activity, and pure Mn3O4-100 showed very inferior catalytic activity towards this reaction. Further detailed characterizations and experimental results revealed that amorphous Fe2O3 plays an important role in expediting the [O] transfer cycle of Mn3+/Mn2+ in Mn3O4, and enhances the oxidation ability and acidity of Fe5Mn5-100. This discovery would provide a new avenue for the atom-economic and environment-friendly industrial synthesis of imine. This journal is
- Cao, Xiao,Gou, Galian,Long, Yu,Luo, Shicheng,Luo, Yutong,Ma, Jiantai,Qin, Jiaheng,Wang, Kaizhi,Wu, Wei
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p. 5628 - 5640
(2020/09/17)
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- Visible light photocatalytic aerobic oxidative synthesis of imines from alcohols and amines on dye-sensitized TiO2
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A general visible light photocatalytic protocol for the synthesis of imines via a two-step one-pot route on alizarin red S (ARS)-sensitized TiO2 was uncovered. This efficient synthesis protocol involves one step of the highly selective formation of aldehydes from the oxidation of alcohols with O2 on ARS-sensitized TiO2 photocatalyst, and a subsequent step of condensation of newly formed aldehydes with various amines on TiO2 to afford imines in one pot. Anatase TiO2 provides a versatile platform for catalytic amounts of ARS (0.67 mol%) to facilitate the electron transfer from dye traversing its conduction band to O2 under green LED irradiation. Moreover, the Lewis acid sites of TiO2 can promote the formation of imines from aldehydes and amines in very high isolated yields. We took advantage of both the photocatalytic and catalytic properties of TiO2 to significantly expand the scope of imines. Our work suggests that the synthetic applications of TiO2 photocatalysis can be achievable under mild conditions by exploring the excellent functionalities of TiO2.
- Xu, Hui,Shi, Ji-Long,Hao, Huimin,Li, Xia,Lang, Xianjun
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p. 128 - 135
(2019/01/04)
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- Visible-light-induced regioselective cross-dehydrogenative coupling of 2 H-indazoles with ethers
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A visible-light-promoted regioselective C(sp2)-H/C(sp3)-H cross-dehydrogenative coupling between 2H-indazoles and ethers has been achieved using a catalytic amount of rose bengal as an organophotoredox-catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant at ambient temperature under aerobic conditions. A variety of C-3 oxyalkylated 2H-indazoles have been synthesized in moderate to good yields. Mechanistic studies suggest a radical pathway of the present reaction.
- Singsardar, Mukta,Laru, Sudip,Mondal, Susmita,Hajra, Alakananda
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p. 4543 - 4550
(2019/04/30)
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- The Generation of Difluoroketenimine and Its Application in the Synthesis of α,α-Difluoro-β-amino Amides
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Fluorine-containing β-amino acids and their derivatives have attracted significant attention due to their importance in life sciences. Herein the previously unknown difluoroketenimine, the analogue of the elusive difluoroketene, has been generated by the
- Zhang, Rui,Zhang, Zhikun,Zhou, Qi,Yu, Lefei,Wang, Jianbo
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supporting information
p. 5744 - 5748
(2019/03/28)
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- Mild and efficient synthesis of secondary aromatic amines by one-pot stepwise reductive amination of arylaldehydes with nitroarenes promoted by reusable nickel nanoparticles
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The one-pot stepwise reductive amination of arylaldehydes with nitroarenes is described, using reusable nickel nanoparticles (Ni-pol) as catalyst and NaBH4 as mild, inexpensive, and safe reducing agent. The proposed catalytic system holds several advantages such as the use of a non-precious and earth-abundant metal, the facile separation of the catalyst from the reaction mixture by centrifugation, excellent stability towards air and moisture, very mild reaction conditions, good recyclability, broad substrate scope with good to excellent yields, and easy scalability (up to 1.0 g). FESEM analyses indicate that the active species are cubic nanocrystals of Ni in the average cross section value of 35 nm with a quite narrow (25–45 nm) and monomodal distribution, which becomes bimodal with the recycling reactions but without agglomeration.
- Fiore, Ambra Maria,Romanazzi, Giuseppe,Dell'Anna, Maria Michela,Latronico, Mario,Leonelli, Cristina,Mali, Matilda,Rizzuti, Antonino,Mastrorilli, Piero
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- Chemoselective Reduction of Imines Catalyzed by Ruthenium(II) Half-Sandwich Complexes: A Mechanistic Study
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Ruthenium half-sandwich complexes ligated to chiral 2-oxazolidinethiones or 2-thiozolidinethiones in the reduction of N-benzylideneaniline using silyl hydrides as reductants has been examined. The chemoselective reduction of imines takes place under mild conditions to afford the corresponding amines in nearly quantitative yield. Mechanistic studies indicate that dissociation of the ancillary ligands generate the active catalyst in all the complexes studied, which is the same species generated by [Ru(p-cymene)(Cl)2]2 under the reaction conditions. This results in the formation of a single catalytic species irrespective of the starting half-sandwich complex. Detailed mechanistic studies involving trapping of intermediates, in situ studies using mass spectrometry and NMR spectroscopy were carried out using the active catalyst generated by [Ru(p-cymene)(Cl)2]2. The mechanism of the reaction is dependent on the number of the hydrogen atoms in the reducing silane. The reaction proceeds via Gade-Hoffman pathway or Zheng-Chan pathway when a dihydro or trihydrosilane is the reductant. However, the use of a monohydrosilane, leads to longer reaction times presumably due to a change in the reaction pathway.
- Reshi, Noor U. Din,Kathuria, Lakshay,Samuelson, Ashoka G.
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p. 2947 - 2955
(2019/06/27)
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- A sustainable catalytic enantioselective synthesis of norstatine derivatives
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Norstatine derivatives are of important value in pharmaceutical science. However, their catalytic asymmetric synthesis is rare. We developed a sustainable method via chiral phosphoric acid (CPA)-[Rh(OAc)2]2 co-catalyzed multi-component reactions (MCR) of diazoacetates with alcohol/water and imines. This method allows us to synthesize a library of 45 norstatines with excellent enanotioselectivites and broad substrate scope which includes anti-α-aryl-norstatines 11-1, anti-α-alkyl-norstatines 11-2, syn-α-hydro-norstatines 11-3 and syn-α-aryl-norstatines 11-4. The sustainability of this method lies in the reliable scalability, improved safety, and reusable [Rh(OAc)2]2 catalyst. The synthetic value of norstatine derivatives was demonstrated by preparing oxazolinone 14, ezetimibe analogue 15, and Taxol C-13 chain 16. Mechanistic study reveals that the synergetic catalysis of CPA and [Rh(OAc)2]2 is essential to maintain chemo- and enantioselectivity. Control experiments support the mechanism where the reactions proceed through the trapping of hyper-reactive oxonium ylides with imines. Shortly, we report herein the sustainable catalytic enantioselective synthesis of both syn- and anti-norstatine derivatives. We believe that this method might shed light on the sustainable synthesis of norstatine derivative-based drug candidates.
- Shi, Taoda,Jing, Changcheng,Qian, Yu,Xu, Xinfang,Alavala, Gopi Krishna Reddy,Lv, Xinxin,Hu, Wenhao
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supporting information
p. 9792 - 9798
(2019/12/02)
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- Iron-Catalyzed Nitrene Transfer Reaction of 4-Hydroxystilbenes with Aryl Azides: Synthesis of Imines via C=C Bond Cleavage
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C=C bond breaking to access the C=N bond remains an underdeveloped area. A new protocol for C=C bond cleavage of alkenes under nonoxidative conditions to produce imines via an iron-catalyzed nitrene transfer reaction of 4-hydroxystilbenes with aryl azides is reported. The success of various sequential one-pot reactions reveals that the good compatibility of this method makes it very attractive for synthetic applications. On the basis of experimental observations, a plausible reaction mechanism is also proposed.
- Peng, Yi,Fan, Yan-Hui,Li, Si-Yuan,Li, Bin,Xue, Jing,Deng, Qing-Hai
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p. 8389 - 8394
(2019/10/16)
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- Synthesis of Secondary Aldimines from the Hydrogenative Cross-Coupling of Nitriles and Amines over Al2O3-Supported Ni Catalysts
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A heterogeneous Ni catalyst was discovered to be active in the synthesis of secondary cross-imines via hydrogenative coupling of nitriles and amines. The mesoporous Al2O3-supported Ni nanoparticles (abbreviated as Ni/m-Al2O3-600, where 600 represents the reduction temperature) were active in hydrogenative coupling of nitriles and amines reaction at 80 °C and 1 bar H2, affording corresponding cross-imines with yields in the range 64.1-98.1%. Density functional theory calculations reveal the hydrogenation of benzonitrile (PhCN) to benzylamine (PhCH2NH2) has higher activation energy than that for hydrogenative cross-coupling of PhCN and RNH2 on the Ni/m-Al2O3-600 catalyst, suggesting the latter reaction is more favorable. The theoretical calculations are in good agreement with our experimental results.
- Zhou, Peng,Jiang, Liang,Wang, Shuguo,Hu, Xun,Wang, Hongming,Yuan, Ziliang,Zhang, Zehui
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p. 8413 - 8423
(2019/09/07)
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- One-pot solvothermal synthesized CoS2@MoS2 nanocomposites for selective reduction coupling reaction to synthesize imines
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Selective reduction coupling of nitroaromatics and aldehydes for imines synthesis has been investigated by using a series of bifunctional CoS2@MoS2 catalysts prepared by one-pot solvothermal method. Under optimal Co/Mo ratio of 0.75 and preparation temperature (180 °C), CoS2@MoS2–180-0.75 catalyst shows 96.5% nitrobenzene conversion, 93.0% imine selectivity and good versatility for substituted nitrobenzene and different aldehydes under mild conditions (60 °C, 1.5 MPa H2). The characterizations reveal that high nitroaromatics hydrogenation activity and good selectivity are mainly due to the formation of CoMoS phase, the coupling reaction between aniline derivatives and aldehydes is achieved by the appropriate acidity of CoS2@MoS2 nanocomposites.
- Han, Wenpeng,Wang, Junwei,Li, Xuekuan,Zhou, Ligong,Yang, Ying,Tang, Mingxing,Ge, Hui
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- A new bifunctional heterogeneous nanocatalyst for one-pot reduction-Schiff base condensation and reduction-carbonylation of nitroarenes
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In this work, synthesis of Pd-NHC-γ-Fe2O3-n-butyl-SO3H and its activity as a bifunctional heterogeneous nanocatalyst containing Pd-NHC and acidic functional groups, are described. This newly synthesized nanomagnetic catalyst is fully characterized by different methods such as FT-IR, XPS, TEM, VSM, ICP and TG analysis. At first, the catalytic activity of Pd-NHC-γ-Fe2O3-n-butyl-SO3H is evaluated for the reduction of nitroarenes in aqueous media using NaBH4 as a clean source of hydrogen generation at ambient temperature. Using the promising results obtained from the nitroarene reduction, this catalytic system is used for two one-pot protocols including reduction-Schiff base condensation and reduction-carbonylation of various nitroarenes. In these reactions the in situ formed amines are further reacted with aldehydes to yield imines or carbonylated to amides. The desired products are obtained in good to high yields in the presence of Pd-NHC-γ-Fe2O3-n-butyl-SO3H as a bifunctional catalyst. The catalyst is reused with the aid of a magnetic bar for up to six consecutive cycles without any drastic loss of its catalytic activity.
- Sobhani, Sara,Chahkamali, Farhad Omarzehi,Sansano, José Miguel
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p. 1362 - 1372
(2019/01/24)
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- Direct reductive coupling of nitroarenes and alcohols catalysed by Co-N-C/CNT@AC
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A non-noble heterogeneous catalyst-a Co, N and C composite encapsulated carbon nanotube grown in situ on the surface of activated carbon (Co-N-C/CNT@AC)-was fabricated via the pyrolysis-reduction process. Co-N-C/CNT@AC catalyzed the reductive coupling of structurally diverse nitroarenes and alcohols to imines and secondary amines under exogenous base- and solvent-free conditions. BET, TEM, SEM, XRD and XPS characterization showed that the exceptional catalytic property of Co-N-C/CNT@AC could be explained by its nanostructure, Co-N and basic N species. Our protocol had advantages of low cost, environment-friendliness, and good applicability. Furthermore, a reaction route of nitroarenes, amines and alcohols as the starting materials was proposed to improve the atom economy of the reductive coupling of nitroarenes with alcohols.
- Liu, Di,Yang, Ping,Zhang, Hao,Liu, Minjie,Zhang, Wenfei,Xu, Dongmei,Gao, Jun
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p. 2129 - 2137
(2019/04/27)
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- Efficient imine synthesis from oxidative coupling of alcohols and amines under air atmosphere catalysed by Zn-doped Al2O3 supported Au nanoparticles
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Direct oxidative coupling of alcohols and amines is regarded as an effective and green approach for imine synthesis under mild conditions. In this work, Zn-doped γ-Al2O3 supported Au nanoparticles was demonstrated as highly active and selective heterogeneous catalyst for a series of imine productions with good to excellent yields, from alcohols and amines via direct oxidative coupling under air atmosphere without extra base additives. Various physicochemical techniques, including ICP-MS, XRD, N2 physisorption, TEM, XPS and CO2-/NH3-TPD, were used to study the properties of the catalysts. Well-dispersed Au0 nanoparticles with a mean size of ca. 2.9 nm were found highly effective in activating alcohols in the presence of reactive amines. The amount of Zn2+ dopant and the calcination temperature of support during catalyst preparation showed crucial impact on tuning the intrinsic activity for oxidation of benzyl alcohol to benzaldehyde (i.e., the rate-determining step for the model reaction), which was disclosed to be related with the active surface oxygen species and the acidic-basic property of support. The 0.4% Au/Zn0.02Al2O3 catalyst calcined at 400 °C exhibited the highest TOF (39.1 h?1) at 60 °C based on a >99% yield to benzylideneaniline among all the ever-reported Au-based catalysts. Moreover, this catalyst could afford 98% yield to benzylideneaniline at only 30 °C and work effectively for the gram-scale synthesis. It also showed considerable stability after five consecutive recycling.
- Wu, Shipeng,Sun, Weixiao,Chen, Junjie,Zhao, Jinghan,Cao, Qiue,Fang, Wenhao,Zhao
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p. 110 - 121
(2019/08/01)
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- Synthesis of Imines via Reactions of Benzyl Alcohol with Amines Using Half-Sandwich (η6-p-cymene) Ruthenium(II) Complexes Stabilised by 2-aminofluorene Derivatives
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A new class of half-sandwich (η6-p-cymene) ruthenium(II) complexes supported by 2-aminofluorene derivatives [Ru(η6-p-cymene)(Cl)(L)] (L?=?2-(((9H-fluoren-2-yl)imino)methyl)phenol (L1), 2-(((9H-fluoren-2-yl)imino)methyl)-3-methoxyphenol (L2), 1-(((9H-fluoren-2-yl)imino)methyl)naphthalene-2-ol (L3) and N-((1H-pyrrol-2-yl)methylene)-9H-fluorene-2-amine (L4)) were synthesized. All compounds were fully characterized by analytical and spectroscopic techniques (IR, UV–Vis, NMR) and also by mass spectrometry. The solid state molecular structures of the complexes [Ru(η6-p-cymene)(Cl)(L2)], [Ru(η6-p-cymene)(Cl)(L3)] and [Ru(η6-p-cymene)(Cl)(L4)] revealed that the 2-aminofluorene and p-cymene moieties coordinate to ruthenium(II) in a three-legged piano-stool geometry. The synthesized complexes were used as catalysts for the dehydrogenative coupling of benzyl alcohol with a range of amines (aliphatic, aromatic and heterocyclic). The reactions were carried out under thermal heating, ultrasound and microwave assistance, using solvent or solvent free conditions, and the catalytic performance was optimized regarding the solvent, the type of base, the catalyst loading and the temperature. Moderately high to very high isolated yields were obtained using [Ru(η6-p-cymene)(Cl)(L4)] at 1?mol%. In general, microwave irradiation produced better yields than the other two techniques irrespective of the nature of the substituents.
- Vinoth, Govindasamy,Indira, Sekar,Bharathi, Madheswaran,Durgadevi, Anandhan,Abinaya, Ravikumar,Alves, Luis G.,Martins, Ana Margarida,Bharathi, Kuppannan Shanmuga
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- Bi-functional catalyst of porous N-doped carbon with bimetallic FeCu for solvent-free resultant imines and hydrogenation of nitroarenes
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The efficient and stable catalyst applied to the transformation of amines into the corresponding imines and hydrogenation of nitroarenes under mild reaction conditions is reported. The catalytic performance of porous N-doped carbon with FeCu (FeCu@NPC) catalyst are tested by aromatic alcohol-based N-alkylated of amines with solvent-free and hydrogenation of nitroarenes via N2H4·H2O. The results proved that the yield of these two reactions are all over 99.9% under optimum condition. Moreover, the synergistic effect of the catalyst for N-alkylated reaction was investigated through the kinetic study. The catalyst can be easily separated from reaction system by an external magnetism, and can be recycled and reutilized for at least 4 runs with conversions are all over 75%. The study of the catalyst indicated that it was suitable for the reactions in industry. Hence, the catalysis process by the inexpensive metals-based catalyst is green and sustainable.
- Wang, Kaizhi,Gao, Wenbing,Jiang, Pengbo,Lan, Kai,Yang, Ming,Huang, Xiaokang,Ma, Lei,Niu, Fang,Li, Rong
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- One-pot synthesis of Pd-promoted Ce-Ni mixed oxides as efficient catalysts for imine production from the direct: N -alkylation of amine with alcohol
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Ce-Ni mixed oxides with different Ni/Ce molar ratios, promoted by a rather low amount of Pd (0.2 wt%), were prepared by a simple one-pot precipitation method. The thus-synthesized CeNiXOY and Pd-CeNiXOY catalysts were applied respectively to the direct N-alkylation of amine and alcohol via oxidative coupling, under O2 in the absence of basic additives. The CeNiXOY catalyst could provide a >99% yield of imine in the model alkylation reaction of aniline with benzyl alcohol at 100 °C. The Pd-promoted Pd-CeNiXOY catalyst surprisingly showed an enhanced imine yield (>99%) at a mild temperature of 60 °C. This catalyst exhibited good reusability, and moreover, demonstrated high performance towards imine synthesis from various amines with alcohols. The presence of Pd species and the Ni/Ce molar ratio showed a synergistic impact on the conversion of aniline, as well as on the product selectivity, which was believed to be related to the improvement on the intrinsic activity of the oxidation of benzyl alcohol to benzaldehyde. Various physicochemical techniques, including ICP-MS, XRD, N2 adsorption-desorption, UV-Raman, H2-TPR, TEM, EPMA and XPS, were employed to study mainly the composition, structure and redox properties of the catalysts. The proportion of Ce3+ species and oxygen vacancies, which can be manipulated by the Ce-Ni redox system and the interaction between Ce and Ni, was crucial to the selective activation of alcohols in the presence of reactive amines. The activation of alcohol on the highly reactive Pd0 species was the other crucial factor.
- Zhang, Mengyuan,Wu, Shipeng,Bian, Longchun,Cao, Qiue,Fang, Wenhao
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p. 286 - 301
(2019/01/28)
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- Method for preparing imine by utilizing copper catalyst to catalyze cross coupling of amine and alcohol
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The invention discloses a method for preparing imine by utilizing a copper catalyst to catalyze cross coupling of amine and alcohol. The method comprises the following steps: under the condition of nooxidant, adopting Cu/Al2O3 as a catalyst to catalyze the cross coupling of the amine and the alcohol so as to prepare the imine. The method disclosed by the invention has beneficial effects that thereaction system is simple, cocatalysts such as organic ligand, alkaline, and free radical of nitroxide do not need to be added, and simultaneously under the condition of no oxidant, the method utilizes Cu/Al2O3 to catalyze cross coupling of the amine and the alcohol so as to prepare the imine; the problem that the imine is easily peroxidated can be effectively solved; in addition, the catalyst Cu/Al2O3 used by the method is simple in preparation, is highly-effective and stable and is low in price.
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Paragraph 0036; 0037; 0039
(2019/02/04)
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- Amorphous Fe2O3 improved [O] transfer cycle of Ce4+/Ce3+ in CeO2 for atom economy synthesis of imines at low temperature
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CeO2 based catalysts have been investigated in various catalytic reactions due to its unique reversible Ce3+/Ce4+ redox pair and physicochemical property, but its poor cycle efficiency and low reservoir limit its wide application in the fine chemicals industry. In this work, a novel amorphous Fe2O3 modified CeO2 catalytic system was developed by a facile co-precipitation method. The as-prepared samples were characterized in detail, and were employed for catalyzing the one-pot synthesis of imine from benzyl alcohol and aniline under air atmosphere at low temperature. The as-prepared sample with molar ratio of Fe:Ce = 8:2 dried at 100 °C (named Fe8Ce2-100) exhibited superhigh activity for atom economy synthesis of imine, which was much higher than the reported CeO2 catalyst, even higher than some noble metal catalysts. It is worth noting that pure amorphous Fe2O3-100 could not catalyze this reaction at all, and both pure CeO2-100 and the mechanical mixed sample with the same molar ratio of Fe:Ce exhibited much more inferior catalytic activity than Fe8Ce2-100. Combining characterization results and the catalytic activities of different catalysts at various reaction conditions, the enhanced catalytic activity of Fe8Ce2-100 could be ascribed to the novel synergistic effect between CeO2 and amorphous Fe2O3. Amorphous Fe2O3 plays the role of engine to greatly improve the [O] transfer cycle of Ce4+/Ce3+, as well as enhances the redox and amphoteric properties of the catalysts. This work firstly determines amorphous Fe2O3 can participate and facilitate the catalytic cycle for organic reaction, and may provide a significant strategy for designing polymetallic oxide catalyst towards organic aerobic transformation.
- Qin, Jiaheng,Long, Yu,Wu, Wei,Zhang, Wei,Gao, Zekun,Ma, Jiantai
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p. 161 - 174
(2019/02/15)
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- H2-Generation from Alcohols by the MOF-Based Noble Metal-Free Photocatalyst Ni/CdS/TiO2@MIL-101
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The synthesis of important classes of chemical compounds from alcohols helps to conserve Earth's fossil carbon resources, since alcohols can be obtained from indigestible and abundantly available biomass. The utilisation of visible light for the activation of alcohols permits alcohol-based C-N and C-C bond formation under mild conditions inaccessible with thermally operating hydrogen liberation catalysts. Herein, we report on a noble metal-free photocatalyst able to split alcohols into hydrogen and carbonyl compounds under inert gas atmosphere without the requirement of electron donors, additives, or aqueous reaction media. The reusable photocatalyst mediates C-N multiple bond formation using the oxidation of alcohols and subsequent coupling with amines. The photocatalyst consists of a CdS/TiO2 heterojunction decorated with co-catalytic Ni nanoparticles and is prepared on size-optimised colloidal metal-organic framework (MOF) crystallites.
- Tilgner, Dominic,Klarner, Mara,Hammon, Sebastian,Friedrich, Martin,Verch, Andreas,De Jonge, Niels,Kümmel, Stephan,Kempe, Rhett
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p. 842 - 847
(2019/08/26)
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