- Continuous flow heterogeneous catalytic reductive aminations under aqueous micellar conditions enabled by an oscillatory plug flow reactor
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Despite the fact that continuous flow processing exhibits well-established technical advances, aqueous micellar chemistry, a field that has proven extremely useful in shifting organic synthesis to sustainable water-based media, has mostly been explored under conventional batch-based conditions. This is particularly because of the fact that the reliable handling of slurries and suspensions in flow has been considered as a significant technical challenge. Herein, we demonstrate that the strategic application of an oscillatory plug flow reactor enables heterogeneous catalytic reductive aminations in aqueous micellar media enhancing mass transport and facilitating process simplicity, stability and scalability. The micellar flow process enabled a broad range of substrates, including amino acid derivatives, to be successfully transformed under reasonably mild conditions utilizing only very low amounts of Pd/C as a readily available heterogeneous catalyst. The preparative capabilities of the process along with the recyclability of the heterogenous catalyst and the aqueous reaction media were also demonstrated. This journal is
- ?tv?s, Sándor B.,Buchholcz, Balázs,Darvas, Ferenc,Kappe, C. Oliver,Novák, Zoltán,Sipos, Gellért,Wernik, Michaela
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supporting information
p. 5625 - 5632
(2021/08/16)
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- Method for realizing oxidative dehydrogenation of nitrogen-containing heterocyclic ring by using biomass-based carbon material
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The invention provides a method for realizing oxidative dehydrogenation of a nitrogen-containing heterocyclic ring by using a biomass-based carbon material, and belongs to the field of organic synthesis. According to the method, the raw materials of the biomass-based carbon material comprise wheat, sorghum, rice, corn straw, wheat straw, peanut shells, sesame shells, bean shells and the like, and are crushed and then ground into powder, the powder is fully mixed with an inorganic alkali, and calcination is performed in an inert gas atmosphere to prepare the biomass-based carbon material; and by using air as an oxygen source, at a temperature of 50-120 DEG C, oxidative dehydrogenation of nitrogen-containing heterocyclic compounds to synthesize quinoline compounds, isoquinoline compounds, acridine compounds, quinazoline compounds, indole compounds, imine compounds, and even quinoline compounds with pharmaceutical activity can be achieved. According to the present invention, easily available wheat flour is adopted as a raw material to prepare a non-metal catalyst, the alkali is not added during the reaction process, and a remarkable industrial application prospect is achieved.
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Paragraph 0010-0011; 0040-0041
(2021/06/26)
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- Discovery of tert-amine-based RORγt agonists
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The nuclear receptor retinoic acid receptor-related orphan receptor gamma-t (RORγt) is a transcription factor regulating Th17 cell differentiation and proliferation from naive CD4+ T cells. Since Th17 cells have demonstrated the antitumor efficacy by eliciting remarkable activation of CD8+ T cells, RORγt agonists could be applied as potential small molecule therapeutics for cancer immunotherapy. Based on the previously reported RORγt agonist 1 and its resolved co-crystal structure, a series of new tertiary amines were designed, synthesized and biologically evaluated, yielding optimal moieties with improved chemical properties and biological responses. The combination of these optimal moieties resulted in identification of novel RORγt agonists such as 8b with further elevated RORγt agonism responses at a target-based level as well as in cell-based assays, which provided some structural knowledge for further optimization of RORγt agonists as small molecule therapeutics for cancer immunotherapy.
- Qiu, Ruomeng,Yu, Mingcheng,Gong, Juwen,Tian, Jinlong,Huang, Yafei,Wang, Yonghui,Xie, Qiong
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- Palladium supported on magnesium hydroxyl fluoride: An effective acid catalyst for the hydrogenation of imines and N-heterocycles
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Palladium catalysts supported on acidic fluorinated magnesium hydroxide Pd/MgF2-x(OH)x were prepared through precipitation or impregnation methods. Applications to the hydrogenation of various aldimines and ketimines resulted in good catalytic activities at mild temperatures using one atmosphere of hydrogen. Quinolines, pyridines and other N-heterocycles were successfully hydrogenated at higher temperature and hydrogen pressure using low palladium loadings and without the use of any acid additive. Such reactivity trend confirmed the positive effect of the Br?nsted and Lewis acid sites from the fluorinated magnesium hydroxide support resulting in the effective pre-activation of N-heterocycle substrates and therefore in the good catalytic activity of the palladium nanoparticles during the hydrogenations. As demonstrated in the hydrogenation of imines, the catalyst was recycled up to 10 times without either loss of activity or palladium leaching. This journal is
- Agbossou-Niedercorn, Francine,Corre, Yann,Dongare, Mohan K.,Kemnitz, Erhard,Kokane, Reshma,Michon, Christophe,Umbarkar, Shubhangi B.
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supporting information
p. 19572 - 19583
(2021/11/04)
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- Poisoning effect of N-containing compounds on performance of Raney nickel in transfer hydrogenation
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The effect of amines, imines and heterocycle compounds on conversion has been studied in transfer hydrogenation of camphor and 2-PrOH catalyzed by Raney nickel. Small amount (5 mol% to nickel) of N-containing compound significantly decreases catalyst activity. It has been shown that the poisoning effect mostly depends on molecular size of amines and heterocyclic compounds. For aniline and cyclohexylamine the dependence of camphor conversion on poison/nickel ratio was obtained. Additionally, benzaldehyde, cinnamaldehyde demonstrated higher reactivity compared corresponding imines under transfer hydrogenation conditions. Obtained data explain low activity of nickel-based catalysts when N-containing compounds are presented in reaction mixture.
- Martyanov, Oleg N.,Philippov, Alexey A.
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- Synthesis of Lactams by Reductive Amination of Carbonyl Derivatives with ω-Amino Fatty Acids under Hydrosilylation Conditions
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An efficient method for the preparation of lactams from ω-amino fatty acids under hydrosilylation is described. A variety of lactams such as pyrrolidinones, piperidinones and 2-azepanones were selectively synthesised in moderate to excellent yields (29 examples, up to 95 % isolated yields) with a good functional group tolerance. Notably, no metallic based catalyst was required to perform this transformation.
- Tongdee, Satawat,Wei, Duo,Wu, Jiajun,Netkaew, Chakkrit,Darcel, Christophe
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p. 5536 - 5539
(2021/08/07)
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- Highly economical and direct amination of sp3carbon using low-cost nickel pincer catalyst
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Developing more efficient routes to achieve C-N bond coupling is of great importance to industries ranging from products in pharmaceuticals and fertilizers to biomedical technologies and next-generation electroactive materials. Over the past decade, improvements in catalyst design have moved synthesis away from expensive metals to newer inexpensive C-N cross-coupling approaches via direct amine alkylation. For the first time, we report the use of an amide-based nickel pincer catalyst (1) for direct alkylation of amines via activation of sp3 C-H bonds. The reaction was accomplished using a 0.2 mol% catalyst and no additional activating agents other than the base. Upon optimization, it was determined that the ideal reaction conditions involved solvent dimethyl sulfoxide at 110 °C for 3 h. The catalyst demonstrated excellent reactivity in the formation of various imines, intramolecularly cyclized amines, and substituted amines with a turnover number (TON) as high as 183. Depending on the base used for the reaction and the starting amines, the catalyst demonstrated high selectivity towards the product formation. The exploration into the mechanism and kinetics of the reaction pathway suggested the C-H activation as the rate-limiting step, with the reaction second-order overall, holding first-order behavior towards the catalyst and toluene substrate.
- Brandt, Andrew,Rangumagar, Ambar B.,Szwedo, Peter,Wayland, Hunter A.,Parnell, Charlette M.,Munshi, Pradip,Ghosh, Anindya
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p. 1862 - 1874
(2021/01/20)
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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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- Nickel?Copper bimetallic mesoporous nanoparticles: As an efficient heterogeneous catalyst for N-alkylation of amines with alcohols
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A bimetallic catalyst (Ni/Cu-MCM-41) is prepared via co-condensation method. The latter is characterized by Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), diffuse reflectance spectroscopy (DRS), and nitrogen adsorption–desorption analysis. Catalytic performance of Ni/Cu-MCM-41 is probed in N-alkylation of amines with alcohols through a hydrogen autotransfer process. Noteworthy, this catalytic system appears very efficient for synthesis of a range of secondary and tertiary amines in good to excellent isolated yields. Moreover, the catalyst is successfully recovered and reused four times without notable decrease in its activity.
- Nasresfahani, Zahra,Kassaee, Mohamad Z.
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- An Efficient Palladium-Catalysed Aminocarbonylation of Benzyl Chlorides
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An improved procedure for the aminocarbonylation of benzyl chloride derivatives using carbon monoxide and either primary or secondary amines has been developed. Studying the competing background alkylation reaction allowed the solvent and base to be selected for a simple catalyst screen, which, in turn, enabled the discovery of a method for the preparation of 2-arylacetamides under mild conditions, with minimal side-products using an inexpensive phosphine ligand. This non-traditional optimisation strategy allowed us to overcome the background alkylation, which has been cited as justification for the development of more complex and less atom-economical approaches.
- Oram, Niall,Richardson, Jeffery,Rilvin-Derrick, Eloise
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p. 369 - 372
(2020/02/27)
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- Two isostructural URJC-4 materials: From hydrogen physisorption to heterogeneous reductive amination through hydrogen molecule activation at low pressure
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Herein, two novel isostructural metal-organic frameworks (MOFs) M-URJC-4 (M = Co, Ni; URJC = "Universidad Rey Juan Carlos") with open metal sites, permanent microposity, and large surface areas and pore volumes have been developed. These novel MOFs, with polyhedral morphology, crystallize in the monoclinic P21/c space group, exhibiting a three-dimensional structure with microporous channels along the c axis. Initially, they were fully characterized and tested in hydrogen (H2) adsorption at different conditions of temperature and pressure. The physisorption capacities of both materials surpassed the gravimetric H2 uptake shown by most MOF materials under the same conditions. On the basis of the outstanding adsorption properties, the Ni-URJC-4 material was used as a catalyst in a one-pot reductive amination reaction using various carbonyl compounds and primary amines. A possible chemical pathway to obtain secondary amines was proposed via imine formation, and remarkable performances were accomplished. This work evidences the dual ability of M-URJC-4 materials to be used as a H2 adsorbent and a catalyst in reductive amination reactions, activating molecular H2 at low pressures for the reduction of C=N double bonds and providing reference structural features for the design of new versatile heterogeneous materials for industrial application.
- Montes-Andrés, Helena,Leo, Pedro,Mu?oz, Antonio,Rodríguez-Diéguez, Antonio,Orcajo, Gisela,Choquesillo-Lazarte, Duane,Martos, Carmen,Martínez, Fernando,Botas, Juan A.,Calleja, Guillermo
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supporting information
p. 15733 - 15740
(2020/11/02)
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- High-Throughput Screening of Reductive Amination Reactions Using Desorption Electrospray Ionization Mass Spectrometry
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This study describes the latest generation of a high-throughput screening system that is capable of screening thousands of organic reactions in a single day. This system combines a liquid handling robot with desorption electrospray ionization (DESI) mass spectrometry (MS) for a rapid reaction mixture preparation, accelerated synthesis, and automated MS analysis. A total of 3840 unique reductive amination reactions were screened to demonstrate the throughputs that are capable with the system. Products, byproducts, and intermediates were all monitored in full-scan mass spectra, generating a complete view of the reaction progress. Tandem mass spectrometry experiments were conducted to verify the identity of the products formed. The amine and electrophile reactivity trends represented in the data match what is expected from theory, indicating that the system accurately models the reaction performance. The DESI results correlated well with those generated using more traditional mass spectrometry techniques like liquid chromatography-mass spectrometry, validating the data generated by the system.
- Cooks, R. Graham,Ferreira, Christina R.,Li, Yangjie,Logsdon, David L.,Paschoal Sobreira, Tiago Jose,Thompson, David H.
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supporting information
p. 1647 - 1657
(2020/10/26)
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- Ruthenium N-Heterocyclic Carbene Complexes for Chemoselective Reduction of Imines and Reductive Amination of Aldehydes and Ketones
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Chemoselective reduction of imines to secondary amines is catalyzed efficiently by tethered and untethered, half-sandwich ruthenium N-heterocyclic carbene (NHC) complexes at room temperature. The untethered Ru-NHC complexes are more efficient as catalysts for the reduction of aldimines and ketimines than the tethered complexes. Using the best untethered complex as a catalyst, electronic and steric demands on the reaction was probed using a series of imines. Chemoselectivity of the catalyst towards imine reduction was tested by performing inter and intramolecular competitive reactions in a variety of ways. The catalyst exhibits a very high TON and TOF under anaerobic conditions.
- Kathuria, Lakshay,Samuelson, Ashoka G.
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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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- Nickel(II) Catalyzed Hydroboration: A Route to Selective Reduction of Aldehydes and N-Allylimines
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A cationic [(iminophosphine)nickel(allyl)]+ complex was found to be sufficiently electrophilic to activate aldehydes and N-allylimines to undergo hydroboration with pinacolborane (HBpin) under mild reaction conditions. The catalyst displayed excellent selectivity toward aldehydes in the presence of ketones. A wide variety of functional groups were tolerated, including halogens, NO2, CN, OMe, and alkenes for both aldehydes and imines. Electron-rich substrates were found to be significantly more reactive than their electron poor counterparts, a feature that was correlated to their enhanced ability to coordinate to the Lewis acidic nickel center.
- Hossain, Istiak,Schmidt, Joseph A. R.
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p. 1877 - 1884
(2020/05/25)
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- Metal-Ligand Cooperation Facilitates Bond Activation and Catalytic Hydrogenation with Zinc Pincer Complexes
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A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facilitating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.
- Rauch, Michael,Kar, Sayan,Kumar, Amit,Avram, Liat,Shimon, Linda J. W.,Milstein, David
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p. 14513 - 14521
(2020/10/13)
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- One-pot, chemoselective synthesis of secondary amines from aryl nitriles using a PdPt-Fe3O4nanoparticle catalyst
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We have developed a new catalytic method for the one-pot, cascade synthesis of unsymmetrical secondary amines via the reductive amination of aryl nitriles with nitroalkanes using a PdPt-Fe3O4 nanoparticle (NP) catalyst. The use of a bimetallic catalyst resulted in enhanced reactivity and selectivity compared to that of either monometallic Pd-Fe3O4 or the Pt-Fe3O4 NP catalyst. Using this bimetallic catalytic system, we were successful in the synthesis of various unsymmetrical secondary amines under mild conditions. However, aryl nitriles containing an electron-donating substituent were rather resistant to the reductive amination, and when hexafluoroisopropanol (HFIP) was used as a co-solvent, the reaction selectivity and yield for unsymmetrical secondary amines increased dramatically. Using the catalyst system, one-pot, gram-scale synthesis of indole was possible from 2-nitrophenylacetonitrile. Due to the magnetic property of the Fe3O4 support, the bimetallic catalyst could easily be recycled using an external magnet at least four times.
- Byun, Sangmoon,Cho, Ahra,Cho, Jin Hee,Kim, B. Moon
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p. 4201 - 4209
(2020/09/23)
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- Highly Efficient and Selective N-Alkylation of Amines with Alcohols Catalyzed by in Situ Rehydrated Titanium Hydroxide
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Catalytic N-alkylation of amines by alcohols to produce desired amines is an important catalytic reaction in industry. Various noble-metal-based homogeneous and heterogeneous catalysts have been reported for this process. The development of cheap non-noble-metal heterogeneous catalysts for the N-alkylation reaction would be highly desirable. Hereby, we propose the N-alkylation of amines by alcohols over a cheap and efficient heterogeneous catalyst-titanium hydroxide. This catalyst provides a selectivity higher than 90% to secondary amines for functionalized aromatic and aliphatic alcohols and amines with high catalytic activity and stability. Mild Br?nsted acidity formed by the continuous rehydration of Lewis acidity excludes the side reactions and deactivation by adsorbed species. The mechanism of the reaction involves dehydration of alcohols to ethers with subsequent C-O bond cleavage by amine with the formation of secondary amine and recovery of alcohol.
- Khodakov, Andrei Y.,Kusema, Bright T.,Niu, Feng,Ordomsky, Vitaly V.,Wang, Qiyan,Yan, Zhen
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p. 3404 - 3414
(2020/03/23)
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- Tertiary amine derivative or salt thereof, preparation method and application thereof
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Belonging to the technical field of chemical medicine, the invention relates to a tertiary amine RORgamma t regulator, in particular to a new tertiary amine compound or salt thereof with RORgamma t inhibition or agonist activity shown as general formula I, a preparation method and a pharmaceutical composition thereof. The tertiary amine compound or a salt thereof provided by the invention can be used for preparation of drugs treating or preventing RORgamma t receptor related diseases.
- -
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Paragraph 0290; 0293; 0294; 0295
(2019/01/24)
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- Colloidal and Nanosized Catalysts in Organic Synthesis: XXIII. Reductive Amination of Carbonyl Compounds Catalyzed by Nickel Nanoparticles in a Plug-Flow Reactor
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Reductive amination of aldehydes and ketones with primary and secondary amines under catalysis with nickel nanoparticles supported on zeolite X, MgO, or activated carbon in the gas phase or in the gas-liquid system in a plug-flow reactor proceeds at atmospheric pressure of hydrogen with the formation of secondary or tertiary amines in high yield.
- Mokhov, V. M.,Nebykov, D. N.,Paputina, A. N.,Popov, Yu. V.,Shishkin, E. V.
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p. 2333 - 2340
(2020/02/25)
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- Reductive C-O, C-N, and C-S Cleavage by a Zirconium Catalyzed Hydrometalation/β-Elimination Approach
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A zirconium catalyzed reductive cleavage of Csp3 and Csp2 carbon-heteroatom bonds is reported that makes use of a tethered alkene functionality as a traceless directing group. The reaction is successfully demonstrated on C-O, C-N, and C-S bonds and proposed to proceed via a hydrozirconation/β-heteroatom elimination sequence of an in situ formed zirconium hydride catalyst. The positional isomerization of the catalyst further enables the cleavage of homoallylic ethers and the removal of terminal allyl and propargyl groups.
- Matt, Christof,K?lblin, Frederic,Streuff, Jan
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p. 6983 - 6988
(2019/09/09)
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- Unlocking the catalytic potential of tris(3,4,5-trifluorophenyl)borane with microwave irradiation
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The catalytic activity of tris(3,4,5-trifluorophenyl)borane has been explored in the 1,2-hydroboration reactions of unsaturated substrates. Under conventional conditions, the borane was found to be active only in the hydroboration of aldehyde, ketone and imine substrates, with alkenes and alkynes not being reduced effectively. The use of microwave irradiation on the other hand has permitted alkenes and alkynes to be hydroborated in good yields.
- Carden, Jamie L.,Gierlichs, Lukas J.,Wass, Duncan F.,Browne, Duncan L.,Melen, Rebecca L.
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p. 318 - 321
(2019/01/09)
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- Mesoporous cobalt/manganese oxide: A highly selective bifunctional catalyst for amine-imine transformations
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Herein, we discuss a heterogeneous catalytic protocol using cobalt doped mesoporous manganese oxide for amine-alcohol cross-coupling to selectively produce symmetric or asymmetric imines. Thorough investigations on the surface chemistry and physical properties of the material revealed its outstanding oxidation-reduction properties and reaction mechanism which was supported by quantum mechanical calculations done by using density functional theory (DFT).
- Dutta, Biswanath,March, Seth,Achola, Laura,Sahoo, Sanjubala,He, Junkai,Shirazi Amin, Alireza,Wu, Yang,Poges, Shannon,Pamir Alpay,Suib, Steven L.
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p. 3180 - 3185
(2018/07/29)
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- Effect of Ancillary Ligand in Cyclometalated Ru(II)-NHC-Catalyzed Transfer Hydrogenation of Unsaturated Compounds
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In an effort to develop efficient Ru(II)-NHC-based catalyst considering their stereoelectronic effect for hydride-transfer reaction, we found that the ancillary NHC ligand can play a significant role in its catalytic performance. This effect is demonstrated by comparing the activity of two different types of orthometalated precatalysts of general formula [(p-cymene)(NHC)RuII(X)] (NHC = an imidazolylidene-based ImNHC, compound 2a-c, or a mesoionic triazolylidene-based tzNHC, compound 4) in transfer hydrogenation of carbonyl substrates. The electron-rich precatalyst, 2c, containing p-OMe-substituted NHC ligand performed significantly better than both unsubstituted complex 2a and p-CF3 substituted electron-poor complex 2b in ketone reduction. Whereas bulky mesoionic triazolylidene ligand containing complex 4 was found to be superior catalyst for aldehyde reduction and the precatalyst 2a is more suitable for the selective transfer hydrogenation of a wide range of aromatic aldimines to amines. To the best of our knowledge, this is the first systematic study on the effect of stereoelectronic tuning of ancillary orthometalated NHC ligand in Ru(II)-catalyzed transfer hydrogenations of various types of unsaturated compounds with broad substrate scope.
- Bauri, Somnath,Donthireddy,Illam, Praseetha Mathoor,Rit, Arnab
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supporting information
p. 14582 - 14593
(2018/11/25)
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- PdAu@MIL-100(Fe) cooperatively catalyze tandem reactions between amines and alcohols for efficient N-alkyl amines syntheses under visible light
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PdAu@MIL-100(Fe), with PdAu alloy nanoparticles of ca. 1.7 nm encapsulated inside MIL-100(Fe) cavities, were prepared via a double-solvent impregnation followed by photoreduction. As compared with bare Pd@MIL-100(Fe), bimetallic PdAu@MIL-100(Fe) showed superior activities for the tandem reactions between amines and alcohols to produce N-alkyl amines under visible-light irradiation, ascribed to the promoting effect of metallic Au in the photocatalytic alcohol-to-aldehyde dehydrogenation. A Pd/Au ratio dependent N-alkylation activity was observed over PdAu@MIL-100(Fe), implying the possibility of synchronizing the reaction rates of two consecutive steps in the N-alkylation reaction, i.e., photocatalytic alcohol-to-aldehyde dehydrogenation and imines hydrogenation, to optimize the whole reaction. This study provides a highly efficient and stable catalytic system for the realization of alkylation of amines via a successful coupling of MOF-based photocatalysis and metal nanoparticle-based hydrogenation. This work also demonstrates that the reaction rates of different catalytic steps in a cascade/tandem reaction can be synchronized for an efficient overall reaction via a rational design of the multifunctional catalysts.
- Wang, Dengke,Pan, Yating,Xu, Lizhi,Li, Zhaohui
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p. 248 - 254
(2018/04/02)
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- Unmodified Fe3O4 nanostructure promoted with external magnetic field: safe, magnetically recoverable, and efficient nanocatalyst for N- and C-alkylation reactions in green conditions
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Transition metal compounds have emerged as suitable catalysts for organic reactions. Magnetic compounds as soft Lewis acids can be used as catalysts for organic reactions. In this report, the Fe3O4 nanostructures were obtained from Fe2+ and Fe3+-salts, under an external magnetic field (EMF) without any protective agent. The X-ray photoelectron spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy tools were used to characterize these magnetic compounds. The two-dimensional (2-D, it showed nanometric size in the two dimensions, nanorod structure) Fe3O4 compound showed high catalytic activity and stability in N- and C-alkylation reactions. A diverse range of N- and C-alkylation products were obtained in moderate to high yield under green and mild conditions in air. Also the N- and C-alkylation products can be obtained with different selectivity and yield by exposure reactions with EMF. Results of alkylation reactions showed that the presence of Fe(II) and Fe(III) species on the surface of magnetic catalysts (phase structure of magnetic compounds) are essential as very cheap active sites. Also, morphology of magnetic catalysts had influence on their catalytic performances. After the reaction, the catalyst/product(s) separation could be easily achieved with an external magnet and more than 95% of catalyst could be recovered. The catalyst was reused at least four times without any loss of its high catalytic activity for N- and C-alkylation reactions.
- Rafiee, Ezzat,Joshaghani, Mohammad,Abadi, Parvaneh Ghaderi-Shekhi
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p. 2503 - 2522
(2018/01/04)
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- Preparation of the Ru3(CO)8-pyridine-alcohol cluster and its use for the selective catalytic transformation of primary to secondary amines
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The synthesis of pyridine alcohol based ruthenium carbonyl clusters Ru3(hep)2(CO)8 (1), Ru3(hpp)2(CO)8 (2), and Ru3(bhmp-H)2(CO)8 (3) {hep-H = 2-(2-hydroxyethyl)pyridine, hpp-H = 2-(3-hydroxypropyl)pyridine and bhmp-H2 = 2,6-bis(hydroxymethyl)pyridine} has been carried out by the reaction of the corresponding pyridine-alcohol ligands with Ru3(CO)12. Clusters 1-3 have been characterized using elemental analysis, NMR, FT-IR, mass spectrometry and single-crystal X-ray structures. The clusters were explored for the selective catalytic transformation of primary amines into secondary amines using alcohols as the mono-alkylating agents via hydrogen transfer reactions. All three display efficient catalytic activity with 1 being the most effective.
- Singh, Ajeet,Mobin, Shaikh M.,Mathur, Pradeep
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p. 14033 - 14040
(2018/11/23)
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- Direct Reductive Amination of Carbonyl Compounds Catalyzed by a Moisture Tolerant Tin(IV) Lewis Acid
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Despite the ever-broadening applications of main-group ‘frustrated Lewis pair’ (FLP) chemistry to both new and established reactions, their typical intolerance of water, especially at elevated temperatures (>100 °C), represents a key barrier to their mainstream adoption. Herein we report that FLPs based on the Lewis acid iPr3SnOTf are moisture tolerant in the presence of moderately strong nitrogenous bases, even under high temperature regimes, allowing them to operate as simple and effective catalysts for the reductive amination of organic carbonyls, including for challenging bulky amine and carbonyl substrate partners. (Figure presented.).
- Sapsford, Joshua S.,Scott, Daniel J.,Allcock, Nathan J.,Fuchter, Matthew J.,Tighe, Christopher J.,Ashley, Andrew E.
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supporting information
p. 1066 - 1071
(2018/01/27)
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- Grouping Effect of Single Nickel?N4 Sites in Nitrogen-Doped Carbon Boosts Hydrogen Transfer Coupling of Alcohols and Amines
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As a new type of heterogeneous catalyst with “homogeneous-like” activity, single-site transition-metal materials are usually treated as integrated but separate active centers. A novel grouping effect is reported for single Ni?N4 sites in nitrogen-doped carbon (Ni/NC), where an effective ligand-stabilized polycondensation method endows Ni/NC nanocatalysts with a high content of single-site Ni up to 9.5 wt %. The enhanced electron density at each single Ni?N4 site promotes a highly efficient hydrogen transfer, which is exemplified by the coupling of benzyl alcohol and aniline into N-benzylaniline with a turnover frequency (TOF) value of 7.0 molN-benzylaniline molmetal?1 h?1; this TOF outpaces that of reported stable non-noble-metal-based catalysts by a factor of 2.
- Su, Hui,Gao, Peng,Wang, Meng-Ying,Zhai, Guang-Yao,Zhang, Jun-Jun,Zhao, Tian-Jian,Su, Juan,Antonietti, Markus,Li, Xin-Hao,Chen, Jie-Sheng
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supporting information
p. 15194 - 15198
(2018/10/31)
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- Expanding Water/Base Tolerant Frustrated Lewis Pair Chemistry to Alkylamines Enables Broad Scope Reductive Aminations
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Lower Lewis acidity boranes demonstrate greater tolerance to combinations of water/strong Br?nsted bases than B(C6F5)3, this enables Si?H bond activation by a frustrated Lewis pair (FLP) mechanism to proceed in the presence of H2O/alkylamines. Specifically, BPh3has improved water tolerance in the presence of alkylamines as the Br?nsted acidic adduct H2O–BPh3does not undergo irreversible deprotonation with aliphatic amines in contrast to H2O–B(C6F5)3. Therefore BPh3is a catalyst for the reductive amination of aldehydes and ketones with alkylamines using silanes as reductants. A range of amines inaccessible using B(C6F5)3as catalyst, were accessible by reductive amination catalysed by BPh3via an operationally simple methodology requiring no purification of BPh3or reagents/solvent. BPh3has a complementary reductive amination scope to B(C6F5)3with the former not an effective catalyst for the reductive amination of arylamines, while the latter is not an effective catalyst for the reductive amination of alkylamines. This disparity is due to the different pKavalues of the water–borane adducts and the greater susceptibility of BPh3species towards protodeboronation. An understanding of the deactivation processes occurring using B(C6F5)3and BPh3as reductive amination catalysts led to the identification of a third triarylborane, B(3,5-Cl2C6H3)3, that has a broader substrate scope being able to catalyse the reductive amination of both aryl and alkyl amines with carbonyls.
- Fasano, Valerio,Ingleson, Michael J.
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supporting information
p. 2217 - 2224
(2017/02/18)
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- Enhanced Catalytic Activity of Iridium(III) Complexes by Facile Modification of C,N-Bidentate Chelating Pyridylideneamide Ligands
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A set of aryl-substituted pyridylideneamide (PYA) ligands with variable donor properties owing to a pronounced zwitterionic and a neutral diene-type resonance structure were used as electronically flexible ligands at a pentamethylcyclopentadienyl (Cp) iridium center. The straightforward synthesis of this type of ligand allows for an easy incorporation of donor substituents such as methoxy groups in different positions of the phenyl ring of the C,N-bidentate chelating PYA. These modifications considerably enhance the catalytic activity of the coordinated iridium center toward the catalytic aerobic transfer hydrogenation of carbonyls and imines as well as the hydrosilylation of phenylacetylene. Moreover, these PYA iridium complexes catalyze the base-free transfer hydrogenation of aldehydes, and to a lesser extent also of ketones. Under standard transfer hydrogenation conditions including base, aldehydes are rapidly oxidized to carboxylic acids rather than reduced to the corresponding alcohol, as is observed under base-free conditions.
- Navarro, Miquel,Smith, Christene A.,Albrecht, Martin
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p. 11688 - 11701
(2017/10/10)
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- Use of Catalytic Static Mixers for Continuous Flow Gas-Liquid and Transfer Hydrogenations in Organic Synthesis
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Catalytic static mixers were used for the continuous flow hydrogenation of alkenes, alkynes, carbonyls, nitro- and diazo-compounds, nitriles, imines, and halides. This technique relies on tubular reactors fitted with 3D printed static mixers which are coated with a catalytic metal layer, either Pd or Ni. Additive manufacturing of the metal mixer scaffold results in maximum design flexibility and is compatible with deposition methods such as metal cold spraying which allow for mass production and linear process scale up. High to full conversion was achieved for the majority of substrates, demonstrating the flexibility and versatility of the catalytic static mixer technology. In the example of an alkyne reduction, the selectivity of the flow reactor could be directed to either yield an alkene or alkane product by simply changing the reactor pressure.
- Hornung, Christian H.,Nguyen, Xuan,Carafa, Antony,Gardiner, James,Urban, Andrew,Fraser, Darren,Horne, Mike D.,Gunasegaram, Dayalan R.,Tsanaktsidis, John
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p. 1311 - 1319
(2017/09/23)
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- REACTIONS OF STANNYL CATIONS
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The present invention relates to a method of reducing, cleaving and/or coupling at least one C=O, C-O, C=C or C=N bond of a compound, using a reagent comprising a stannyl cation.
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Page/Page column 22
(2018/01/17)
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- Ruthenium-catalyzed deaminative redistribution of primary and secondary amines
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A ruthenium-hydride complex, [Ru(H)(Cl)(CO)(PCy3)2], was found to be active in the highly selective redistribution of primary and secondary amines bearing an α-hydrogen atom. This new deaminative coupling of amines enables the highly selective synthesis of secondary amines from primary amines and of tertiary amines from secondary amines with the evolution of ammonia. A preliminary mechanistic view of this novel reaction based on catalytic experiments using NMR methods confirms the synthetic observations.
- Kostera,Wyrzykiewicz,Pawlu?,Marciniec
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supporting information
p. 11552 - 11555
(2017/09/18)
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- Cs2CO3-Promoted Direct N-Alkylation: Highly Chemoselective Synthesis of N-Alkylated Benzylamines and Anilines
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Herein is described an efficient and chemoselective method for the synthesis of diversely substituted secondary amines in yields up to 98 %. Direct mono-N-alkylation of primary benzylamines and anilines with a wide range of alkyl halides is promoted by a cesium base in the absence of any additive or catalyst. The basicity and solubility of cesium carbonate in anhydrous N,N-dimethylformamide not only enables mono-N-alkylation of primary amines but also suppresses undesired dialkylation of the desired amines.
- Castillo, Juan-Carlos,Orrego-Hernández, Jessica,Portilla, Jaime
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p. 3824 - 3835
(2016/08/20)
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- A process for preparing amine compound using carbon-supported cobalt-rhodium nanoparticel catalyzed hydrogen-free recuctive amination
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The present invention relates to hydrogen-free reductive amination of an aldehyde and/or ketone and an amine and/or nitroarene using cobalt-rhodium heterometal nanoparticles supported on carbon as a non-homogeneous catalyst. According to the present invention, it is possible to carry out amination under significantly lower pressure as compared to the reductive amination carried out in the presence of a conventional rhodium or ruthenium catalyst. In addition, there is no need for using an additional ligand, acid or base. Further, it is possible to use water generated in a reaction system by a water-gas shift reaction as a hydrogen source with no use of an external hydrogen source, and thus to use a solvent without purification. Thus, it is possible to simplify the reaction procedure. The catalyst system according to the present invention provides a simple method for preparing secondary and tertiary amines from various aldehydes and amines.
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-
Paragraph 0066; 0068; 0073
(2017/04/25)
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- Heterogeneous cobalt catalysts for reductive amination with H2: General synthesis of secondary and tertiary amines
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Heterogeneous Co@NC catalysts were prepared, characterized and applied for the reductive amination of aldehydes and ketones with H2 gas. The Co catalyst Co@NC (800-2 h) was found to be active and selective for the reductive amination of aldehydes and ketones using H2 gas. Thus, general synthesis of secondary and tertiary amines was developed by the Co-catalyzed reductive amination with H2 gas, and various secondary and tertiary amines can be obtained in high yields. Moreover, a practical synthesis of N-substituted isoindolinones was also presented by a one step process with the Co@NC (800-2 h) catalyst. The Co@NC (800-2 h) catalyst is reusable at least five times without evident loss of activity.
- Mao, Fei,Sui, Dejun,Qi, Zhengliang,Fan, Haipeng,Chen, Rizhi,Huang, Jun
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p. 94068 - 94073
(2016/10/22)
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- New trans dichloro (triphenylphosphine)platinum(II) complexes containing N-(butyl),N-(arylmethyl)amino ligands: Synthesis, cytotoxicity and mechanism of action
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Some new platinum(II) complexes have been prepared, of general formula trans-[PtCl2(PPh3){NH(Bu)CH2Ar}], where the dimension of the Ar residue in the secondary amines has been varied from small phenyl to large pyrenyl group. The obtained complexes, tested in vitro towards a panel of human tumor cell lines showed an interesting antiproliferative effect on both cisplatin-sensitive and -resistant cells. For the most cytotoxic derivative 2a the investigation on the mechanism of action highlighted the ability to induce apoptosis on resistant cells and interestingly, to inhibit the catalytic activity of topoisomerase II.
- Dalla Via, Lisa,García-Argáez, Aída Nelly,Agostinelli, Enzo,Belli Dell'Amico, Daniela,Labella, Luca,Samaritani, Simona
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p. 2929 - 2937
(2016/06/13)
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- Stereocontrolled Synthesis of β-Lactams within [2]Rotaxanes: Showcasing the Chemical Consequences of the Mechanical Bond
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The intramolecular cyclization of N-benzylfumaramide [2]rotaxanes is described. The mechanical bond of these substrates activates this transformation to proceed in high yields and in a regio- and diastereoselective manner, giving interlocked 3,4-disubstituted trans-azetidin-2-ones. This activation effect markedly differs from the more common shielding protection of threaded functions by the macrocycle, in this case promoting an unusual and disfavored 4-exo-trig ring closure. Kinetic and synthetic studies allowed us to delineate an advantageous approach toward β-lactams based on a two-step, one-pot protocol: an intramolecular ring closure followed by a thermally induced dethreading step. The advantages of carrying out this cyclization in the confined space of a benzylic amide macrocycle are attributed to its anchimeric assistance.
- Martinez-Cuezva, Alberto,Lopez-Leonardo, Carmen,Bautista, Delia,Alajarin, Mateo,Berna, Jose
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supporting information
p. 8726 - 8729
(2016/07/30)
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- NHC-Catalyzed Benzylic Csp3–H Bond Activation of Alkylarenes and N-Benzylamines for the Synthesis of 3H-Quinazolin-4-ones: Experimental and Theoretical Study
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An N-heterocyclic carbene catalyzed benzylic Csp3–H bond activation of alkylarenes and N-benzylamines under metal-free conditions was developed. This organocatalyzed oxidative transformation afforded the corresponding carbonyl derivatives in good to excellent yields. A variety of alkylarenes and N-benzylamines were tolerated under the optimized reaction conditions. The established method was further extended to the synthesis of biologically important 3H-quinazolin-4-ones in good yields. For example, NPS 53574, a potent calcium receptor antagonist, was successfully synthesized by using this oxidative protocol. DFT studies show that the benzylic C–H bond activation proceeds through the nucleophilic attack of the free carbene on the benzylic carbon atom.
- Alanthadka, Anitha,Devi, E. Sankari,Nagarajan, Subbiah,Sridharan, Vellaisamy,Suvitha, Ambigapathy,Maheswari, C. Uma
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supporting information
p. 4872 - 4880
(2016/10/13)
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- Ruthenium-Catalyzed Selective Hydroboration of Nitriles and Imines
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Ruthenium-catalyzed hydroboration of nitriles and imines is attained using pinacolborane with unprecedented catalytic efficiency. Chemoselective hydroboration of nitriles over esters is also demonstrated. A simple [Ru(p-cymene)Cl2]2 complex (1) is used as a catalyst precursor, which upon reaction with pinacolborane in situ generates the monohydrido-bridged complex [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] 2. Further oxidative addition of pinacolborane to intermediate 2 leading to the formation of mononuclear ruthenium hydride species is suggested. Mass spectral analysis of the reaction mixture and independent experiments with phosphine-ligated ruthenium complexes indicated the involvement of mononuclear ruthenium intermediates in the catalytic cycle. Consecutive intramolecular 1,3-hydride transfers from the ruthenium center to coordinated nitrile and boronate imine ligands, leading to the reduction and resulting in the formation of diboronate amines, are proposed as a plausible reaction mechanism.
- Kaithal, Akash,Chatterjee, Basujit,Gunanathan, Chidambaram
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p. 11153 - 11163
(2016/11/28)
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- Coupling MOF-based photocatalysis with Pd catalysis over Pd@MIL-100(Fe) for efficient N-alkylation of amines with alcohols under visible light
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Pd nanoparticles with an average size of 1.7 nm confined inside a MIL-100(Fe) cavity (Pd@MIL-100(Fe)) were prepared via double-solvent impregnation combined with a photoreduction process. Due to efficient coupling of photocatalytic dehydrogenation and Pd-based hydrogenation, the resultant Pd@MIL-100(Fe) showed significantly superior performance in light-induced N-alkylation of amines with alcohols over Pd/MIL-100(Fe), in which larger Pd nanoparticles (6–12 nm) deposited on the external surface of MIL-100(Fe) were prepared via a conventional single-solvent impregnation followed by a similar photoreduction process. Kinetic studies and controlled experiments revealed that the whole N-alkylation reaction is limited by the photocatalytic alcohol-to-aldehyde dehydrogenation reaction. This is the first demonstration of light-induced N-alkylation of amines by alcohols over M/MOFs nanocomposites and also highlights the great potential of using M/MOFs nanocomposites as multifunctional catalysts for light-induced organic syntheses.
- Wang, Dengke,Li, Zhaohui
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p. 151 - 157
(2018/03/29)
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- Mild Metal-Free Hydrosilylation of Secondary Amides to Amines
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The combination of amide activation by Tf2O with B(C6F5)3-catalyzed hydrosilylation with TMDS constitutes a method for the one-pot reduction of secondary amides to amines under mild conditions. The method displays a broad applicability for the reduction of many types of substrates, and shows good compatibility and excellent chemoselectivity for many sensitive functional groups. Reductions of a multifunctionalized α,β-unsaturated amide obtained from another synthetic methodology, and a C-H functionalization product produced the corresponding amines in good to excellent yield. Chemoselective reduction of enantiomeric pure (ee >99%) tetrahydro-5-oxo-2-furaneamides yielded 5-(aminomethyl)dihydrofuran-2(3H)-ones in a racemization-free manner. The latter were converted in one pot to N-protected 5-hydroxypiperidin-2-ones, which are building blocks for the synthesis of many natural products. Further elaboration of an intermediate led to a concise four-step synthesis of -epi-pseudoconhydrine.
- Huang, Pei-Qiang,Lang, Qi-Wei,Wang, Yan-Rong
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p. 4235 - 4243
(2016/06/09)
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- Hydrogen-Free Cobalt-Rhodium Heterobimetallic Nanoparticle-Catalyzed Reductive Amination of Aldehydes and Ketones with Amines and Nitroarenes in the Presence of Carbon Monoxide and Water
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Cobalt-rhodium heterobimetallic nanoparticle-catalyzed reductive amination of aldehydes and ketones with amines in the presence of 5 atm carbon monoxide without an external hydrogen source has been developed. Water added and generated in situ produces hydrogen via a water-gas-shift reaction. The reaction can be extended to the tandem reduction of aldehydes and ketones with nitroarenes. The catalytic system is stable under the reaction conditions and could be reused eight times without losing any catalytic activity. (Chemical Equation Presented).
- Park, Jang Won,Chung, Young Keun
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p. 4846 - 4850
(2015/08/18)
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- An efficient catalytic reductive amination: A facile one-pot access to 1,2-dihydropyrrolo[3,4-b]indol-3(4H)-ones by using B(C 6 F 5 ) 3 /NaBH 4
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An efficient combination of B(C6F5)3 and NaBH4 was developed for direct reductive amination of aldehydes. A wide range of functional groups such as ester, nitro, nitrile, halogen, alkene, heterocycles were tolerated. Also, acid sensitive protecting groups like TBDMS and TBDPS were not affected. In addition, the present methodology was extended for tandem amination-amidation of 3-formyl-indole-2-carboxylic acids with substituted anilines to afford 1,2-dihydropyrrolo[3,4-b]indol-3(4H)-ones. [Figure not available: see fulltext.]
- Nagarsenkar, Atulya,Prajapti, Santosh Kumar,Babu, Bathini Nagendra
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p. 711 - 716
(2015/06/17)
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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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- Efficient hydrosilylation of imines using catalysts based on iridium(iii) metallacycles
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Ir(iii) metallacycles were applied as catalysts for the hydrosilylation of various ketimines and aldimines with sodium tetrakis[(3,5-trifluoromethyl)phenyl]borate, NaBArF24, as an additive. By using a slight excess of the organosilane reagent, the reactions proceeded rapidly and efficiently, at low catalyst loadings and at room temperature. Several examples of cationic Ir(iii) catalysts could be synthesised, characterized and tested. In situ-generated catalysts proved to be more active as compared to isolated ones and species with non-coordinating BArF24 counterion gave the highest catalytic activities.
- Corre,Iali,Hamdaoui,Trivelli,Djukic,Agbossou-Niedercorn,Michon
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p. 1452 - 1458
(2015/04/14)
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- Nano-sized NiLa2O4 spinel-NaBH4-mediated reduction of imines to secondary amines
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Nano-sized NiLa2O4 spinel was produced by thermal decomposition of Ni-La compounds via a sol-gel method. The well-crystallized spinel structure was formed after calcination at 750 °C. The physicochemical properties of the spinel were investigated using differential thermal analysis, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and particle size distribution analysis. The results show that the nanoparticles have regular shapes with well-defined crystal faces and consist of uniform quasi-spherical crystallites of average size 40 nm. The refined unit cell parameters are a = 3.861205 ? and c = 12.6793 ?. This new nano-sized NiLa2O4 spinel is an efficient heterogeneous catalyst for the selective conversion of imines to the corresponding secondary amines in the presence of NaBH4 as a reducing agent, in good to excellent yields. All the reactions were completely chemoselective at room temperature and had relatively short reaction times. Secondary amines with different aryl groups, including those bearing electron-withdrawing or electron-donating groups, were obtained under the optimum reaction conditions. The catalyst was readily recovered and was recycled four times with no significant loss of catalytic activity.
- Shiri, Ali,Soleymanpour, Faezehy,Eshghi, Hossein,Khosravi, Iman
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p. 1191 - 1196
(2015/09/01)
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- A conjugated ketone as a catalyst in alcohol amination reactions under transition-metal and hetero-atom free conditions
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Here, we show the results of a molecular-defined conjugated ketone catalyzed alcohol amination reaction. Under the optimized reaction conditions, the yields to the desired products reached 98%. The reaction mechanism and kinetic study supposed that carbonyl-hydroxyl groups are the catalytically active sites, and the transfer-hydrogenation reactions progress via the recycling of carbonyl and hydroxyl groups. The catalytic process shows promise as an efficient and economic route for alcohol amination reactions.
- Dai, Xingchao,Cui, Xinjiang,Deng, Youquan,Shi, Feng
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p. 43589 - 43593
(2015/05/27)
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- Reductive amination of aldehydes and ketones catalyzed by deep eutectic solvent using sodium borohydride as a reducing agent
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Different derivatives of aldehydes/ketones were subjected under reductive amination reaction in the presence of ChCl/Urea as a green and biocompatible catalyst. Sodium borohydride was used as a reducing agent. Secondary amines were achieved with high selectivities and yields.
- Saberi, Dariush,Akbari, Jafar,Mahdudi, Samaneh,Heydari, Akbar
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p. 208 - 210
(2014/05/06)
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