- Heterogeneous Ru/TiO2for hydroaminomethylation of olefins: multicomponent synthesis of amines
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Synthesizing aminesviathe hydroaminomethylation (HAM) reaction of olefins, a multicomponent reaction, has been regarded as one of the most attractive methods compared with the traditional methods considering the atom economy and environmental friendliness. However, the use of homogeneous catalysts, complex ligands containing diphosphine or nitrogen, and base or acid additives has severely hampered the utilization of these methods. Herein, an efficient heterogeneous Ru/TiO2-catalyzed HAM reaction of olefins is developed without any additives. Various amines, including secondary and tertiary amines, can be successfully obtained from olefins including aromatic and aliphatic olefins. Systematic studies demonstrate the lower electron density of Ruδ+and the higher number of acid sites of Ru/TiO2, leading to the high HAM reaction activity of olefins. Most importantly, nitrobenzene derivatives can also be transformed to the corresponding products over Ru/TiO2in excellent yields.
- An, Jinghua,Gao, Zhuyan,Wang, Yehong,Zhang, Zhixin,Zhang, Jian,Li, Lu,Tang, Bo,Wang, Feng
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supporting information
p. 2722 - 2728
(2021/04/21)
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- Easy Access to Versatile Catalytic Systems for C?H Activation and Reductive Amination Based on Tetrahydrofluorenyl Rhodium(III) Complexes
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On the basis of the 1,2,3,4-tetrahydrofluorenyl ligand, a simple approach was developed to new effective rhodium catalysts for the construction of C?C and C?N bonds. The halide compounds [(η5-tetrahydrofluorenyl)RhX2]2 (2
- Kharitonov, Vladimir B.,Runikhina, Sofiya A.,Nelyubina, Yulia V.,Muratov, Dmitry V.,Chusov, Denis,Loginov, Dmitry A.
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supporting information
p. 10903 - 10912
(2021/06/28)
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- Tris(pyrazolyl)borate rhodium complexes. Application for reductive amination and esterification of aldehydes in the presence of carbon monoxide
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The halide complexes TpRhCl2(MeOH) and TpMe2RhI2(CO) (Tp = hydrotris-(pyrazolyl)borate; TpMe2 = hydrotris-(3,5-dimethylpyrazolyl)borate) were synthesized by reactions of RhCl3 with K[Tp] in methanol and TpMe2Rh(CO)2 with iodine, respectively. Reactions of TpMe2RhCl2(MeOH) and TpMe2RhI2(CO) with 1,10-phenanthroline afford the phenanthroline derivatives [TpMe2Rh(phen)X]+ (X = Cl, I). The structures of TpRhCl2(MeOH) and TpRhI2(CO) were determined by X-ray diffraction. Tris(pyrazolyl)borate rhodium complexes effectively catalyze the reductive amination and the reductive esterification of aldehydes in the presence of carbon monoxide.
- Kharitonov, Vladimir B.,Ostrovskii, Vladimir S.,Nelyubina, Yulia V.,Muratov, Dmitry V.,Chusov, Denis,Loginov, Dmitry A.
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- NEW METHOD FOR THE SYNTHESIS OF UNSYMMETRICAL TERTIARY AMINES
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Disclosed is a new method for the synthesis of unsymmetrical tertiary amines using alcohol and an imine, and to new tertiary amines.
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Page/Page column 0089
(2020/08/25)
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- Fluorene Complexes of Group 9 Metals: Fluorene Effect and Application for Reductive Amination
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The η6-fluorene cyclopentadienyl complexes [(η5-C5R5)M(η6-fluorene)](SbF6)2 (1: M = Co, R = Me; 2a: M = Rh, R = H; 2b: M = Ir, R = H) were synthesized by the iodide abstraction f
- Kharitonov, Vladimir B.,Podyacheva, Evgeniya,Nelyubina, Yulia V.,Muratov, Dmitry V.,Peregudov, Alexander S.,Denisov, Gleb,Chusov, Denis,Loginov, Dmitry A.
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supporting information
p. 3151 - 3158
(2019/08/26)
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- Cobalt-Catalyzed Reductive Alkylation of Amines with Carboxylic Acids
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Direct reductive alkylation of amines with carboxylic acid is carried out by using an inexpensive, air-stable cobalt/triphos catalytic system with molecular hydrogen as the reductant. This efficient synthetic method proceeds through reduction and condensation, followed by reduction of the in situ-generated imine into the amine in a green catalytic process.
- Emayavaramban, Balakumar,Chakraborty, Priyanka,Sundararaju, Basker
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p. 3089 - 3093
(2018/12/11)
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- Iron-Catalyzed Regioselective α-C-H Alkylation of N-Methylanilines: Cross-Dehydrogenative Coupling between Unactivated C(sp3)-H and C(sp3)-H Bonds via a Radical Process
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The iron-catalyzed α-C-H alkylation of N-methylanilines without any directing group by cross-dehydrogenative coupling between unactivated C(sp3)-H and C(sp3)-H bonds has been established for the first time, which provides a good complement to C(sp3)-H activation reactions and expands the field of Fe-catalyzed C-H functionalizations. Many different C(sp3)-H bonds in cyclic alkanes, cyclic ethers, and toluene derivatives can be used as coupling partners. Mechanistic investigations including the radical reaction process, the main role of various reagents, and the kinetic isotope effect experiment were also described.
- Li, Ze-Lin,Sun, Kang-Kang,Wu, Peng-Yu,Cai, Chun
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p. 6830 - 6839
(2019/06/14)
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- Planar-Chiral [2.2]Paracyclophane-Based Pyridonates as Ligands for Tantalum-Catalyzed Hydroaminoalkylation
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By using planar chiral [2.2]paracyclophane-containing N,O-chelating ligands for tantalum-catalyzed hydroaminoalkylation, one of the most versatile catalytic systems for this reaction to date was obtained. Convenient Csp3?Csp3 bond fo
- Braun, Carolin,Nieger, Martin,Br?se, Stefan,Schafer, Laurel L.
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p. 5264 - 5268
(2019/05/21)
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- Indenyl rhodium complexes. Synthesis and catalytic activity in reductive amination using carbon monoxide as a reducing agent
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Indenyl-ligated rhodium(III) catalyst [(η5-indenyl)RhX2]n (1) is reported for the synthesis of alkylated amines via catalytic reductive amination using carbon monoxide as a reducing agent. Water as a solvent was found to b
- Runikhina, Sofiya A.,Arsenov, Mikhail A.,Kharitonov, Vladimir B.,Sovdagarova, Elizaveta R.,Chusova, Olga,Nelyubina, Yulia V.,Denisov, Gleb L.,Usanov, Dmitry L.,Chusov, Denis,Loginov, Dmitry A.
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supporting information
p. 106 - 112
(2017/11/27)
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- Efficient Synthesis of Amines by Iron-Catalyzed C=N Transfer Hydrogenation and C=O Reductive Amination
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Here we report the catalytic transfer hydrogenation (CTH) of non-activated imines promoted by a Fe-catalyst in the absence of Lewis acid co-catalysts. Use of the (cyclopentadienone)iron complex 1, which is much more active than the classical ‘Kn?lker complex’ 2, allowed to reduce a number of N-aryl and N-alkyl imines in very good yields using iPrOH as hydrogen source. The reaction proceeds with relatively low catalyst loading (0.5–2 mol%) and, remarkably, its scope includes also ketimines, whose reduction with a Fe-complex as the only catalyst has little precedents. Based on this methodology, we developed a one-pot CTH protocol for the reductive amination of aldehydes/ketones, which provides access to secondary amines in high yield without the need to isolate imine intermediates. (Figure presented.).
- Facchini, Sofia Vailati,Cettolin, Mattia,Bai, Xishan,Casamassima, Giuseppe,Pignataro, Luca,Gennari, Cesare,Piarulli, Umberto
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p. 1054 - 1059
(2018/01/27)
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- Synthesis of the cyclopentadienone rhodium complexes and investigation of their catalytic activity in the reductive amination of aldehydes in the presence of carbon monoxide
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Reaction of bis(p-tolyl-propargyl)-tosylamide with [(cod)RhCl]2in the presence of CO gives the cyclopentadienone complex [(Cpd’)Rh(CO)Cl]n(Cpd’ = TsN(CH2)2C4(Tol)2CO). Its dissolution in DM
- Pototskiy, Roman A.,Afanasyev, Oleg I.,Nelyubina, Yulia V.,Chusov, Denis,Kudinov, Alexander R.,Perekalin, Dmitry S.
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supporting information
p. 6 - 11
(2017/03/02)
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- A segmented flow platform for on-demand medicinal chemistry and compound synthesis in oscillating droplets
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We report an automated flow chemistry platform that can efficiently perform a wide range of chemistries, including single/multi-phase and single/multi-step, with a reaction volume of just 14 μL. The breadth of compatible chemistries is successfully demonstrated and the desired products are characterized, isolated, and collected online by preparative HPLC/MS/ELSD.
- Hwang, Ye-Jin,Coley, Connor W.,Abolhasani, Milad,Marzinzik, Andreas L.,Koch, Guido,Spanka, Carsten,Lehmann, Hansjoerg,Jensen, Klavs F.
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p. 6649 - 6652
(2017/07/10)
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- Cyclobutadiene Metal Complexes: A New Class of Highly Selective Catalysts. An Application to Direct Reductive Amination
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A catalyst of a new type, cyclobutadiene complex [(C4Et4)Rh(p-xylene)]PF6, was found to promote selective reductive amination in the presence of carbon monoxide under mild conditions (1-3 bar, 90 °C). The reaction demonstr
- Afanasyev, Oleg I.,Tsygankov, Alexey A.,Usanov, Dmitry L.,Perekalin, Dmitry S.,Shvydkiy, Nikita V.,Maleev, Victor I.,Kudinov, Alexander R.,Chusov, Denis
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p. 2043 - 2046
(2016/03/15)
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- Ruthenium-catalyzed reductive amination without an external hydrogen source
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A ruthenium-catalyzed reductive amination without an external hydrogen source has been developed using carbon monoxide as the reductant and ruthenium(III) chloride (0.008-2 mol %) as the catalyst. The method was applied to the synthesis of antianxiety agent ladasten.
- Kolesnikov, Pavel N.,Yagafarov, Niyaz Z.,Usanov, Dmitry L.,Maleev, Victor I.,Chusov, Denis
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supporting information
p. 173 - 175
(2015/01/30)
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- Reductive Transformations of Carbonyl Compounds Catalyzed by Rhodium Supported on a Carbon Matrix by using Carbon Monoxide as a Deoxygenative Agent
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An efficient method for the rhodium on carbon matrix catalyzed preparation of secondary and tertiary amines, cyanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds was developed, including a convenient procedure for the tandem formal reductive addition of acetonitrile to aldehydes. The catalyst could be reused, and at least three consecutive reaction cycles were performed with comparable efficiency. The method was shown to be compatible with functional groups prone to reduction by hydrogen and complex hydrides. Beyond the matrix: An efficient method for the rhodium on carbon matrix catalyzed preparation of secondary and tertiary amines, cyanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds is developed, including a convenient procedure for the tandem formal reductive addition of acetonitrile to aldehydes. TON=turnover number.
- Yagafarov, Niyaz Z.,Usanov, Dmitry L.,Moskovets, Alexey P.,Kagramanov, Nikolai D.,Maleev, Victor I.,Chusov, Denis
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p. 2590 - 2593
(2015/09/15)
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- CATALYST COMPOUNDS
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The present invention relates to an iridium-based catalyst compound for hydrogenating reducible moieties, especially imines and iminiums, the catalyst compounds being defined by the formula: (Formula (I)) where ring B is a conjugated ring system with one or more substituents. The catalysts of the invention are particularly effective in reductive amination procedures which involve the in situ generation of the imine or iminium under reductive hydrogenative conditions.
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Paragraph 0293; 0295
(2015/03/16)
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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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- Reductive amination without an external hydrogen source
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A method of reductive amination without an external hydrogen source is reported. Carbon monoxide is used as the reductant. The reaction proceeds efficiently for a variety of carbonyl compounds and amines at low catalyst loadings and is mechanistically interesting as it does not seem to involve molecular hydrogen. Look, no H2! Reductive amination without an external hydrogen source has been developed using carbon monoxide as the reductant and rhodium acetate (0.2-1mol %) as catalyst. The method tolerates a variety of functional groups and provides target amines in good to excellent yields.
- Chusov, Denis,List, Benjamin
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supporting information
p. 5199 - 5201
(2014/05/20)
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- Solvent- and catalyst-free direct reductive amination of aldehydes and ketones with Hantzsch ester: Synthesis of secondary and tertiary amines
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A facile and rapid method for the parallel synthesis of a series of secondary and tertiary amines by the direct reductive amination of aldehydes and ketones with Hantzsch ester under solvent- and catalyst-free has been developed. The scope and limitation of this method are described.
- Nguyen, Quynh Pham Bao,Kim, Taek Hyeon
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p. 4938 - 4943
(2013/07/25)
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- Molecular iodine catalyzed transfer hydrogenation: Reduction of aldimines, ketimines, and α-imino esters
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An efficient and practical protocol for the reduction of aldimines, ketimines, and α-imino esters in the presence of catalytic amount of molecular iodine with Hantzsch ester at ambient temperature afforded the corresponding amines in excellent yields.
- Bachu, Prabhakar,Zhu, Chen,Akiyama, Takahiko
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supporting information
p. 3977 - 3981
(2013/07/25)
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- A highly active cyclometallated iridium catalyst for the hydrogenation of imines
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A cyclometallated iridium complex containing an imino ligand has been shown to catalyse the hydrogenation of imines. The catalyst is highly active and selective for imino bonds, with a wide variety of imines being hydrogenated in less than 1 hour at a substrate/catalyst (S/C) ratio of 2000 at 20 bar H 2 pressure and 75 °C.
- Villa-Marcos, Barbara,Tang, Weijun,Wu, Xiaofeng,Xiao, Jianliang
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supporting information
p. 6934 - 6939
(2013/10/08)
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- FeCl2-promoted cleavage of the unactivated C-C bond of alkylarenes and polystyrene: Direct synthesis of arylamines
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Ironing it out: An efficient and convenient nitrogenation strategy involving C-C bond cleavage for the straightforward synthesis of versatile arylamines is presented. Various alkyl azides and alkylarenes, including the common industrial by-product cumene, react using this protocol. Moreover, this method provides a potential strategy for the degradation of polystyrene. Copyright
- Qin, Chong,Shen, Tao,Tang, Conghui,Jiao, Ning
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p. 6971 - 6975
(2012/09/25)
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- Transfer hydrogenation of imines with carboxyl-tailed benzothiazoline as readily removable hydrogen donor
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A benzothiazoline bearing 4-carboxyphenyl group at 2-position was developed as an efficient hydrogen donor for the transfer hydrogenation reaction. Introduction of the carboxyl group significantly facilitated the removal of the residual benzothiazoline an
- Zhu, Chen,Akiyama, Takahiko
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supporting information; experimental part
p. 416 - 418
(2012/02/05)
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- S-Benzyl isothiouronium chloride as a recoverable organocatalyst for the direct reductive amination of aldehydes
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The direct reductive amination of aldehydes using S-benzyl isothiouronium chloride as a recoverable organocatalyst for the activation of the imine intermediate through hydrogen bonding is described. A mild and operationally simple fragment coupling procedure was accomplished with a wide range of aldehydes as well as amines in good to excellent yields. In addition, the S-benzyl isothiouronium chloride catalyst was easily recovered by simple filtration and reused without any drop in its efficiency.
- Nguyen, Quynh Pham Bao,Kim, Taek Hyeon
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supporting information; experimental part
p. 5004 - 5007
(2011/10/07)
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- Br?nsted acid catalyzed reductive amination with benzothiazoline as a highly efficient hydrogen donor
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Reductive amination of aldehyde and amine proceeded smoothly in the presence of benzothiazoline as efficient hydrogen source by means of 20 mol% trifluoroacetic acid to give the corresponding amines in excellent yields. Hydrogen-donor abilities of benzothiazoline, benzimidazoline, and benzoxazoline were compared. Georg Thieme Verlag Stuttgart - New York.
- Zhu, Chen,Akiyama, Takahiko
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supporting information; experimental part
p. 1251 - 1254
(2011/06/28)
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- An efficient, recoverable fluorous organocatalyst for direct reductive amination of aldehydes
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A commercially available perfluorooctyl aniline and phenyl isothiocyanate were reacted under mild conditions to give 1-[4-(perfluorooctyl)phenyl]-3- phenylthiourea as an analogue of thiourea-based organocatalyst. This fluorous organocatalyst was successfully employed to direct reductive amination of aldehydes. It could be readily separated from reaction product by fluorous solid phase extraction for direct use.
- Huang, Yi-Bo,Yi, Wen-Bin,Cai, Chun
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experimental part
p. 879 - 882
(2010/10/01)
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- Conjugated imines and iminium salts as versatile acceptors of nucleophiles
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Growing interests in nitrogen-containing molecules involving bioactive and functional materials have stimulated the recent development of synthetic methodologies where nucleophilic addition reactions to imino carbons are utilized in crucial steps. This article summarizes double nucleophilic addition reactions with α,β-unsaturated aldimines, addition reactions using alkynyl imines, "umpoled" reactions of α-imino esters, and the use of iminium salts as reactive electrophiles. The Royal Society of Chemistry 2009.
- Shimizu, Makoto,Hachiya, Iwao,Mizota, Isao
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scheme or table
p. 874 - 889
(2009/07/10)
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- Rapid microwave-assisted reductive amination of ketones with anilines
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Using microwave technology, a new protocol has been developed that improves the reaction rate and overall efficiency of the direct reductive amination of ketones with anilines. When using sodium triacetoxyborohydride as the reducing agent, high product yi
- Bailey, Helen V.,Heaton, Wesley,Vicker, Nigel,Potter, Barry V. L.
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p. 2444 - 2448
(2008/02/10)
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- Direct and indirect reductive amination of aldehydes and ketones with solid acid-activated sodium borohydride under solvent-free conditions
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A simple and convenient procedure for reductive amination of aldehydes and ketones using sodium borohydride activated by boric acid, p-toluenesulfonic acid monohydrate or benzoic acid as reducing agent under solvent-free conditions is described.
- Byung, Tae Cho,Sang, Kyu Kang
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p. 5725 - 5734
(2007/10/03)
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- A selective reductive amination of aldehydes by the use of Hantzsch dihydropyridines as reductant
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Direct reductive amination of an aldehyde was carried out using a Hantzsch dihydropyridine as the reductant in the presence of a catalytic amount of scandium triflate. The reaction was highly selective towards aldehydes over ketones, and other reducible functional groups did not affect the reaction.
- Itoh, Takashi,Nagata, Kazuhiro,Miyazaki, Michiko,Ishikawa, Hiroyuki,Kurihara, Ayako,Ohsawa, Akio
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p. 6649 - 6655
(2007/10/03)
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- Iminomalonate as a convenient electrophilic amination reagent for grignard reagents
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Diethyl 2-[N-(p-methoxyphenyl)imino]malonate underwent amination reactions with alkyl Grignard reagents to give N-aklylation products in good yields. The obtained N-alkylation products were readily converted into N-alkyl-panisidines by the oxidative removal of the malonate moiety. The p-methoxyphenyl group was subsequently deprotected to give primary amines.
- Niwa, Yasuki,Takayama, Kazuki,Shimizu, Makoto
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p. 1819 - 1825
(2007/10/03)
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- Reductive amination of aldehydes and ketones by a Hantzsch dihydropyridine using scandium triflate as a catalyst
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Direct reductive amination of aldehydes and ketones was carried out using a Hantzsch dihydropyridine as a reducing agent in the presence of a catalytic amount of a Lewis acid.
- Itoh, Takashi,Nagata, Kazuhiro,Kurihara, Ayako,Miyazaki, Michiko,Ohsawa, Akio
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p. 3105 - 3108
(2007/10/03)
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- A new synthetic method for the reduction of imines by samarium-induced reaction
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Samarium metal induced reduction of the imines towards the synthesis of secondary amines has been investigated.
- Banik,Ghatak,Samajdar,Basu,Hackfeld,Banik,Zegrocka,Becker
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p. 1134 - 1139
(2007/10/03)
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- Kinetics and mechanism of the aminolysis of cycloalkylmethyl arenesulfonates
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Nucleophilic substitution reactions of cycloalkylmethyl arenesulfonates (CmH2n-1 CH2OSO2C6H4Z) with anilines (XC6H4NH2) in methanol at 65.0 °C were studied. The reactivity order (n=4>6>7>5) reflects largely the order of steric effect of the ring size (SEs term) except for n=5, which exhibits the least reactivity. This reversal of the order for n=5 is considered to result from large rate retardation due to polar effect of the ρ*σ* term. Application of the Taft equation to the rate data for n=5 and 6 gives ρ=17·4 and 5=2·3 with correlation coefficient of 0·90. The σ* values for n=4 and 7 are estimated to be - 0·23 and - 0·11, respectively. The positive ρxz values of ca 0·3 are consistent with previous results for the reactions at primary reaction centers.
- Oh, Hyuck Keun,Song, Se Jeong,Jo, Dong-Soo,Lee, Ikchoon
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- Selective synthesis of N-(cyclohexylmethyl)-N-alkylamines from primary amines and pimelaldehyde using tetracarbonylhydridoferrate, HFe(CO)4-, as a reducing reagent
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Treatment of primary amines with pimelaldehyde in the presence of tetracarbonyl-hydridoferrate, HFe(CO)4- at room temperature under atmospheric pressure of CO for 24 hours gave selectively corresponding N-(cyclohexylmethyl)-N-alkylam
- Shim,Kwon,Doh,Kim,Kim
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p. 105 - 106
(2007/10/02)
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