- 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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Read Online
- 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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Read Online
- Enhancing the efficiency of the ruthenium catalysts in the reductive amination without an external hydrogen source
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Catalytic reductive reactions are essential for laboratory and industrial-scale organic synthesis. However, the nowadays trend is the development of new, progressively more complicated reducing systems, which hinders the application of such highly efficie
- Afanasyev, Oleg I.,Chusov, Denis,Fatkulin, Artemy R.,Tsygankov, Alexey A.
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p. 404 - 409
(2022/01/13)
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- Phosphine ligands in the ruthenium-catalyzed reductive amination without an external hydrogen source
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A systematic study of the phosphine additives influence on the activity of a ruthenium catalyst in reductive amination without an external hydrogen source was carried out. [CymeneRuCl2]2 was used as a reference catalyst, and a broad set of phosphines including Alk3P, Alk2ArP, Ar3P and X3P was screened. Three complexes of general formula (Cymene)RuCl2PR3 were isolated in a pure form, and their catalytic activity was compared with the in situ generated complexes. Nonhindered triarylphosphines with electron acceptor groups were found to be the most perspective activating agents, increasing the activity of the catalyst approx. six times, Alk2ArP ligands have less noticeable influence, while trialkylphosphines strongly deactivate the ruthenium catalyst.
- Makarova, Maria,Afanasyev, Oleg I.,Kliuev, Fedor,Nelyubina, Yulia V.,Godovikova, Maria,Chusov, Denis
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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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- Carbon monoxide-driven osmium catalyzed reductive amination harvesting WGSR power
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Herein, we present the first example of Os-catalyzed efficient reductive amination under water-gas shift reaction conditions. The developed catalytic systems are formedin situin aqueous solutions, employ as small as 0.0625 mol% osmium and are capable of delivering reductive amination products for a broad range of aliphatic and aromatic carbonyl compounds and amines. The scope of the reaction, active catalytic systems, possible limitations of the method and DFT-supported mechanistic considerations are discussed in detail in the manuscript.
- Afanasyev, Oleg I.,Biriukov, Klim O.,Chusov, Denis,Godovikova, Maria,Loginov, Dmitry A.,Nelyubina, Yulia V.,Tsygankov, Alexey A.,Vasilyev, Dmitry V.,Vinogradov, Mikhail M.
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p. 4922 - 4930
(2021/07/26)
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- Alkyl formates as reagents for reductive amination of carbonyl compounds
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Alkyl formates in the presence of basic additives can serve as a reagent in the direct reductive amination of carbonyl compounds. The developed procedure can be applied to various aldehydes and ketones with electron donating and electron withdrawing groups.
- Afanasyev, Oleg I.,Cherkashchenko, Ilia,Kuznetsov, Anton,Kliuev, Fedor,Semenov, Sergey,Chusova, Olga,Denisov, Gleb,Chusov, Denis
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p. 112 - 113
(2020/03/03)
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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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- Hydrogen-Borrowing Amination of Secondary Alcohols Promoted by a (Cyclopentadienone)iron Complex
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Thanks to a highly active catalyst, the scope of the (cyclopentadienone)iron complex-promoted 'hydrogen-borrowing' (HB) amination has been expanded to secondary alcohols, which had previously been reported to react only in the presence of large amounts of co-catalysts. A range of cyclic and acyclic secondary alcohols were reacted with aromatic and aliphatic amines giving fair to excellent yields of the substitution products. The catalyst was also able to promote the cyclization of diols bearing a secondary alcohol group with primary amines to generate saturated N-heterocycles.
- Aiolfi, Francesco,Bai, Xishan,Cettolin, Mattia,Dal Corso, Alberto,Gennari, Cesare,Piarulli, Umberto,Pignataro, Luca
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p. 3545 - 3555
(2019/09/09)
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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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- Direct Aryl C?H Amination with Primary Amines Using Organic Photoredox Catalysis
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The direct catalytic C?H amination of arenes is a powerful synthetic strategy with useful applications in pharmaceuticals, agrochemicals, and materials chemistry. Despite the advances in catalytic C?H functionalization, the use of aliphatic amine coupling partners is limited. Described herein is the construction of C?N bonds, using primary amines, by direct C?H functionalization with an acridinium photoredox catalyst under an aerobic atmosphere. A wide variety of primary amines, including amino acids and more complex amines are competent coupling partners. Various electron-rich aromatics and heteroaromatics are useful scaffolds in this reaction, as are complex, biologically active arenes. We also describe the ability to functionalize arenes that are not oxidized by an acridinium catalyst, such as benzene and toluene, thus supporting a reactive amine cation radical intermediate.
- Margrey, Kaila A.,Levens, Alison,Nicewicz, David A.
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supporting information
p. 15644 - 15648
(2017/11/20)
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- Fine-Bubble-Based Strategy for the Palladium-Catalyzed Hydrogenation of Nitro Groups: Measurement of Ultrafine Bubbles in Organic Solvents
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Fine bubbles of hydrogen were employed as a new reaction medium for the autoclave-free gas-liquid-solid multiphase hydrogenation of nitro groups on a multigram scale. Furthermore, ultrafine bubbles were examined by nanoparticle-tracking analysis in organic solvents.
- Mase, Nobuyuki,Nishina, Yuki,Isomura, Shogo,Sato, Kohei,Narumi, Tetsuo,Watanabe, Naoharu
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supporting information
p. 2184 - 2188
(2017/09/26)
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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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- The synthesis of sterically hindered amines by a direct reductive amination of ketones
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An atom-economical methodology for the synthesis of sterically hindered tertiary amines was developed, which is based on complementary Rh- and Ru-catalyzed direct reductive amination of ketones with primary and secondary amines using carbon monoxide as a deoxygenating agent.
- Yagafarov, Niyaz Z.,Kolesnikov, Pavel N.,Usanov, Dmitry L.,Novikov, Valentin V.,Nelyubina, Yulia V.,Chusov, Denis
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supporting information
p. 1397 - 1400
(2016/01/25)
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- Nickel(II) complex covalently anchored on core shell structured SiO2@Fe3O4 nanoparticles: A robust and magnetically retrievable catalyst for direct one-pot reductive amination of ketones
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A robust and efficient core shell structured magnetically retrievable nickel nanocatalytic system was fabricated via the covalent immobilization of 2-acetyl furan on the surface of an amine functionalized silica coated magnetic nanosupport followed by its metallation with nickel acetate. The newly synthesized magnetic silica based organic-inorganic hybrid nanocatalyst (Ni-ACF@Am-SiO2@Fe3O4) was systematically affirmed using several physico-chemical characterization tools such as FT-IR, XRD, VSM, SEM, TEM, EDS, ED-XRF and AAS. Thereafter, the catalytic performance of this Ni-ACF@Am-SiO2@Fe3O4 nanocatalyst was investigated in the one-pot reductive amination of ketones using NaBH4 as the reductant under neat conditions. The developed core shell magnetic silica based nickel nanocatalyst successfully afforded a structurally diverse range of secondary amines with high turnover frequency (TOF) and excellent conversion percentage. Additionally, it was found that this catalyst could not only be retrieved from the reaction vessel within a fraction of seconds using an external magnet but also be recycled for multiple runs without any discernible loss in its activity that rendered this protocol superior to all the previously established methodologies for the one-pot synthesis of substituted amines. Besides, some of the other fascinating features of this methodology that made it a potential candidate for addressing various economic and environmental concerns were ambient reaction conditions, broad substrate scope, simple workup procedure, shorter reaction time and cost effectiveness.
- Sharma, Rakesh Kumar,Dutta, Sriparna,Sharma, Shivani
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p. 2089 - 2101
(2016/03/19)
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- Iron-catalyzed transfer hydrogenation of imines assisted by an iron-based Lewis acid
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An iron-catalyzed transfer hydrogenation of N-aryl and N-alkyl imines using isopropanol as the hydrogen donor is reported for the first time. A combination of two iron complexes serving different roles is the key for the success of this catalytic system. As a result, an environmentally friendly and precious metal-free transfer hydrogenation of imines has been developed. The use of a suitable co-catalyst as an activator not only led to efficient transfer hydrogenation, but also showed potential in enantioselective transformation.
- Pan, Hui-Jie,Ng, Teng Wei,Zhao, Yu
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p. 5490 - 5493
(2016/07/06)
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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; 0072; 0075
(2017/04/25)
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- Alkylation of Amines with Alcohols and Amines by a Single Catalyst under Mild Conditions
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An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono- and bis-alkylated amines can be obtained with high selectivity. In particular, methanol can be used as the alkylating reagent, affording N-methylated products selectively. A strong solvent effect is observed for the reaction.
- Zou, Qingzhu,Wang, Chao,Smith, Jen,Xue, Dong,Xiao, Jianliang
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supporting information
p. 9656 - 9661
(2015/06/30)
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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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- 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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- Iron-catalyzed amination of alcohols assisted by Lewis acid
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An efficient Lewis acid-assisted, iron-catalyzed amination of alcohols using borrowing hydrogen methodology was developed. In particular, silver fluoride was identified to be a highly effective additive to overcome the low efficiency in the amination of secondary alcohols catalyzed by Kn?lker's complex.
- Pan, Hui-Jie,Ng, Teng Wei,Zhao, Yu
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supporting information
p. 11907 - 11910
(2015/07/20)
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- C- and N-Selective Grignard Addition Reactions of α-Aldimino Esters in the Presence or Absence of Zinc(II) Chloride: Synthetic Applications to Optically Active Azacycles
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Highly practical synthetic methods were developed for the C- and N-selective Grignard addition reactions of N-4-MeOC6H4-protected α-aldimino esters in the presence or absence of zinc(II) chloride. Diastereoselective C-alkyl addition, tandem C-alkyl addition-N-alkylation, and some transformations to synthetically useful optically active azacycles were demonstrated. (Chemical Equation Presented).
- Hatano, Manabu,Yamashita, Kenji,Ishihara, Kazuaki
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p. 2412 - 2415
(2015/05/27)
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- B(C6F5)3 mediated arene hydrogenation/transannulation of para-methoxyanilines
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The stoichiometric reaction of para-methoxyanilines and B(C6F5)3 under H2 results in reduction of the N-bound phenyl ring(s), and subsequent transannular ring closure with elimination of methanol, affording the respective 7-azabicyclo[2.2.1]heptane derivatives.
- Longobardi, Lauren E.,Mahdi, Tayseer,Stephan, Douglas W.
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supporting information
p. 7114 - 7117
(2015/04/27)
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- C-selective and diastereoselective alkyl addition to β,γ-alkynyl-α-imino esters with zinc(II)ate complexes
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Since umpolung α-imino esters contain three electrophilic centers, regioselective alkyl addition with traditional organometallic reagents has been a serious problem in the practical synthesis of versatile chiral α-amino acid derivatives. An unusual C-alkyl addition to α-imino esters using a Grignard reagent (RMgX)-derived zinc(II)ate was developed. Zinc(II)ate complexes consist of a Lewis acidic [MgX]+moiety, a nucleophilic [R3Zn]- moiety, and 2[MgX2]. Therefore, the ionically separated [R3Zn]- selectively attacks the imino carbon atom, which is most strongly activated by chelation of [MgX]+. In particular, chiral β,γ-alkynyl-α-imino esters can strongly promote highly regio- and diastereoselective C-alkylation because of structural considerations, and the corresponding optically active α-quaternary amino acid derivatives are obtained within 5 minutes in high to excellent yields.
- Hatano, Manabu,Yamashita, Kenji,Mizuno, Mai,Ito, Orie,Ishihara, Kazuaki
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supporting information
p. 2707 - 2711
(2015/03/04)
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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 formulas: where ring B is either itself polycyclic, or ring B together with R is polycyclic. The catalysts of the invention are particularly effective in reductive amination procedures 10 which involve the in situ generation of the imine or iminium under reductive hydrogenative conditions.
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Paragraph 0314; 0326
(2015/03/28)
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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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- Synthesis, reactivities, and catalytic properties of iodo-bridged polymeric iridium complexes with flexible carbon chain-bridged bis(tetramethylcyclopentadienyl) ligands
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Dinuclear iridium complexes [(C5Me4)(CH 2)n(C5Me4)][Ir(COD)]2 (2a: n = 2; 2b: n = 3; 2c: n = 4) are obtained from the reactions of the corresponding dilithium salts Li2/sub
- Tan, Xing,Li, Bin,Xu, Shansheng,Song, Haibin,Wang, Baiquan
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p. 3253 - 3261
(2013/07/19)
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- Use of primary amines for the selective n-alkylation of anilines by a reusable heterogeneous catalyst
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Traditionally, anilines can be alkylated with reactive alkyl halides but now more safe reagents such as alcohols or even amines can be used. To overcome the limits of homogeneous catalysis for aniline N-alkylation, we have developed a protocol that employs simple Pd/C as a heterogeneous catalyst under microwave dielectric heating. The process, based on the easy Pd-mediated oxidation of primary amines to imines followed by aniline addition, is characterized by a high atom economy as ammonia is the only other product of the reaction. This kind of aniline alkylation with amines has been carried out both in ionic liquid medium using [bmim]PF6 or in a more traditional solvent such as THF where the catalyst could be successfully recycled more times. The reusability of the catalyst was further confirmed by using material recycled from the amination in a standard alkene hydrogenation without loss of efficiency. Georg Thieme Verlag Stuttgart New York.
- Linciano, Pasquale,Pizzetti, Marianna,Porcheddu, Andrea,Taddei, Maurizio
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p. 2249 - 2254
(2013/11/06)
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- Fast reductive amination by transfer hydrogenation "on water"
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Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8. In comparison with that in organic solvents, the reductive amination in an aqueous phase is faster, and the molar ratio of the substrate to the catalyst (S/C) can be set as high as 1×105, the highest S/C value ever reported in reductive amination reactions. The catalyst is easy to access and the reaction is operationally simple, allowing a wide range of ketones and aldehydes to react with various amines in high yields. The protocol provides a practical and environmental friendly new method for the synthesis of amine compounds. Greener amine synthesis: A versatile reductive amination protocol has been developed. By using an iridium catalyst in water, a broad range of ketones and aldehydes react with amines to afford various new amines in good yields (see scheme), with molar ratios of the substrate to the catalyst (S/C) as high as 1×10 5. The pH of the reaction solution plays a key role, regulating both the catalytic activity and the selectivity. Copyright
- Lei, Qian,Wei, Yawen,Talwar, Dinesh,Wang, Chao,Xue, Dong,Xiao, Jianliang
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supporting information
p. 4021 - 4029
(2013/04/10)
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- Cobalt-catalyzed electrophilic amination of arylzincs with N-chloroamines
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Roles reversed: An efficient cobalt-catalyzed electrophilic amination of arylzinc reagents has been achieved. A variety of functionalized arylzincs and N-chloroamines were coupled under mild conditions (see scheme). Both secondary and tertiary arylamines were obtained in moderate to excellent yields. Copyright
- Qian, Xin,Yu, Zailu,Auffrant, Audrey,Gosmini, Corinne
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supporting information
p. 6225 - 6229
(2013/07/05)
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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 formulas: where ring B is either itself polycyclic, or ring B together with R is polycyclic. The catalysts of the invention are particularly effective in reductive amination procedures 10 which involve the in situ generation of the imine or iminium under reductive hydrogenative conditions.
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Paragraph 00163; 00175
(2013/11/05)
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- Tertiary alcohols by tandem β-carbolithiation and N→C aryl migration in enol carbamates
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Enol carbamates (O-vinylcarbamates) derived from aromatic or α,β-unsaturated compounds and bearing an N-aryl substituent undergo carbolithiation by nucleophilic attack at the (nominally nucleophilic) β position of the enol double bond. The resulting carbamate-stabilized allylic, propargylic, or benzylic organolithium rearranges with N→C migration of the N-aryl substituent, creating a quaternary carbon α to O. The products may be readily hydrolyzed to yield multiply branched tertiary alcohols in a one-pot tandem reaction, effectively a polarity-reversed nucleophilic β-alkylation-electrophilic α-arylation of an enol equivalent.
- Fournier, Anne M.,Clayden, Jonathan
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supporting information; experimental part
p. 142 - 145
(2012/02/14)
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- Reductive N -alkylation of nitroarenes: A green approach for the N-alkylation of natural products
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A simple, mild, cost-effective, and green approach for the reductive mono-N-alkylation of nitroarenes has been developed. HOAc/Zn are utilized as the reducing system together with a carbonyl compound as an alkyl source in methanol. Excellent yields were obtained with stoichiometric control of mono- over dialkylated products. Application to five complex natural products demonstrated the practical utility of the method.
- Wahba, Amir E.,Hamann, Mark T.
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experimental part
p. 4578 - 4585
(2012/06/30)
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- Selective cross-coupling of amines by alumina-supported palladium nanocluster catalysts
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Al2O3-supported Pd nanoclusters with an average particle size of 1.8 nm act as a reusable catalyst for the selective cross-coupling of amines. The reaction is a structure-sensitive reaction, demanding coordinatively unsaturated Pd atoms on a metallic nanocluster. The support also affects the activity, an amphoteric oxide (Al2O 3) is most effective. The Royal Society of Chemistry.
- Shimizu, Ken-Ichi,Shimura, Katsuya,Ohshima, Keiichiro,Tamura, Masazumi,Satsuma, Atsushi
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supporting information; experimental part
p. 3096 - 3100
(2011/12/04)
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- Selective copper-promoted cross-coupling of aromatic amines with alkyl boronic acids
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A simple copper-promoted N-monoalkylation of anilines that utilizes alkyl boronic acids as the alkylating partner is presented. The reaction is carried out in refluxing dioxane, and it allows a number of structurally and electronically diverse anilines to be functionalized in a single step. A broad study was carried out to demonstrate the utility of this new methodology for the preparation of phenethylanilines.
- Larrosa, Marta,Guerrero, César,Rodríguez, Ramón,Cruces, Jacobo
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supporting information; experimental part
p. 2101 - 2105
(2010/10/03)
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- Zinc-promoted, iridium catalyzed reductive alkylation of primary amines with aliphatic ketones in aqueous medium
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The reductive alkylation of primary aromatic and aliphatic amines with aliphatic ketones has been achieved in aqueous acidic medium using commercially available, non-activated zinc dust catalyzed by a very small quantity of iridium bromide. Anilines react well in aqueous formic acid, whereas monoalkylamines require 1,4-dioxane as a co-solvent and sulfuric acid as the proton source. A plausible mechanism via low-valent iridium hydride species is proposed.
- da Silva, Renato A.,Bieber, Lothar W.
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scheme or table
p. 689 - 691
(2010/04/02)
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- Design and synthesis of novel dihydroquinoline-3-carboxylic acids as HIV-1 integrase inhibitors
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Previously, we discovered linomide analogues as novel HIV-1 integrase (IN) inhibitors. Here, to make possible structure-activity relationships, we report on the design and synthesis of a series of substituted dihydroquinoline-3-carboxylic acids. The crystal structure of the representative compound 2c has also been solved. Among the eight new analogues, 2e showed a potency in inhibiting IN strand transfer catalytic activity similar to the reference diketo acid inhibitor L-731,988 (IC50 = 0.9 μM vs. 0.54 μM, for 2e and L-731,988, respectively). Furthermore, none of the compounds showed significant cytotoxicity in two tested cancer cell lines. These compounds represent an interesting prototype of IN inhibitors, potentially involved in a metal chelating mechanism, and further optimization is warranted.
- Sechi, Mario,Rizzi, Giuseppe,Bacchi, Alessia,Carcelli, Mauro,Rogolino, Dominga,Pala, Nicolino,Sanchez, Tino W.,Taheri, Laleh,Dayam, Raveendra,Neamati, Nouri
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experimental part
p. 2925 - 2935
(2009/09/05)
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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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- Novel benzodiazepine photoaffinity probe stereoselectively labels a site deep within the membrane-spanning domain of the cholecystokinin receptor
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An understanding of the molecular basis of drug action provides opportunities for refinement of drug properties and for development of more potent and selective molecules that act at the same biological target. In this work, we have identified the active
- Hadac, Elizabeth M.,Dawson, Eric S.,Darrow, James W.,Sugg, Elizabeth E.,Lybrand, Terry P.,Miller, Laurence J.
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p. 850 - 863
(2007/10/03)
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- COMPOUNDS AND THERAPEUTICAL USE THEREOF
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Disclosed are 4-arylamino-quinazolines and analogs thereof effective as activators of caspases and inducers of apoptosis. The compounds of this invention are useful in the treatment of a variety of clinical conditions in which uncontrolled growth and spread of abnormal cells occurs.
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Page 173-174
(2008/06/13)
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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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- Electrophilic amination with iminomalonate
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Diethyl N-anisyliminomalonate has been found to be an excellent electrophilic amination reagent for Grignard reagents to give N-alkylated products in good yields, and subsequent air oxidation affords N-alkylanisidines.
- Niwa, Yasuki,Takayama, Kazuki,Shimizu, Makoto
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p. 5473 - 5476
(2007/10/03)
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- A novel and efficient approach to mono-N-alkyl anilines via addition of Grignard reagents to aryl azides
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Mono-N-alkyl anilines were obtained in high yields within a short reaction time when various aromatic azides were reacted with alkyl magnesium halides at room temperature.
- Sampath Kumar,Subba Reddy,Anjaneyulu,Yadav
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p. 8305 - 8306
(2007/10/03)
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- Use of 1,5-benzo?b!1,4-diazepines to control gastric emptying
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A method of controlling gastric emptying in patients having an early non-insulin-dependent diabetic condition and exhibiting rapid gastric emptying comprising the administration of an effective gastric emptying controlling amount of a compound of Formula
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- METHOD OF INDUCING CHOLECYSTOKININ AGONIST ACTIVITY USING 1,4-BENZODIAZEPINE COMPOUNDS
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A method of inducing a Cholescystokinin-A receptor agonist response in a mammal by administering a compound of formula (I), STR1 where R 1 is C 1-C 6 alkyl, C 3-6 cycloalkyl, phenyl, or substituted phenyl; R 2 is C 3-6 alkyl, C 3-6 cycloalkyl, C 3-6 alkenyl, benzyl, phenylC 1-3 alkyl or substituted phenyl; or NR 1 R 2 together form 1,2,3,4-tetrahydroquinoline or benzazepine mono-, di-, or trisubstituted independently with C 1-6 alkyl, C 1-6 alkoxy or halogen substituents; n is an integer selected from the grouping consisting of 0, 1,2 or 3; p is the integer 0 or 1; q is the integer 0 or 1; r is the integer 0 or 1, provided that when q is 0 then r is 0; R 3, R 4, R 5 and R 8 are selected from a variety of substituents; X is nitrogen, nitroso or R 8 ; m is an integer selected from the group consisting of 0, 1, 2 or 3; Y and Z are hydrogen or halogen, novel intermediates, a pharmaceutical composition for treating obesity, gall bladder stasis, disorders of pancreatic secretion, methods for such treatment and processes for preparing compounds of formula (I).
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- CCK OR GASTRIN MODULATING 5-HETEROCYCLIC-1, 5 BENZODIAZEPINES
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Compounds of general formula (I) and physiologically salts thereof, processes for their preparation and their use as modulators of the effects of gastrin and CCK.
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- Optimization of 3-(1H-Indazol-3-ylmethyl)-1,5-benzodiazepines as potent, orally active CCK-A agonists
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We previously described a series of 3-(1H-indazol-3-ylmethyl)-1,5- benzodiazepine CCK-A agonists exemplified by compound 1 (GW 5823), which is the first reported binding selective CCK-A full agonist demonstrating oral efficacy in a rat feeding model. In this report we describe analogs of compound 1 designed to explore changes to the CS and N1 pharmacophores and their effect on agonist activity and receptor selectivity. Agonist efficacy in this series was affected by stereoelectronic factors within the C3 moiety. Binding affinity for the CCK-A vs CCK-B receptor showed little dependence on the structure of the C3 moiety but was affected by the nature of the second substituent at CS. Structure-activity relationships at the N1- anilidoacetamide 'trigger' moiety within the C3 indazole series were also investigated. Both agonist efficacy and binding affinity within this series were modulated by variation of substituents on the Nl-anilidoacetamide moiety. Evaluation of several analogs in an in vivo mouse gallbladder emptying assay revealed compound 1 to be the most potent and efficacious of all the analogs tested. The pharmacokinetic and pharmacodynamic profile of 1 in rats is also discussed.
- Henke, Brad R.,Aquino, Christopher J.,Birkemo, Larry S.,Croom, Dallas K.,Dougherty Jr., Robert W.,Ervin, Gregory N.,Grizzle, Mary K.,Hirst, Gavin C.,James, Michael K.,Johnson, Michael F.,Queen, Kennedy L.,Sherrill, Ronald G.,Sugg, Elizabeth E.,Suh, Edward M.,Szewczyk, Jerzy W.,Unwalla, Rayomand J.,Yingling, Jeff,Willson, Timothy M.
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p. 2706 - 2725
(2007/10/03)
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- Discovery of 1,5-benzodiazepines with peripheral cholecystokinin (CCK-A) receptor agonist activity. 1. Optimization of the agonist "trigger"
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Directed screening of compounds selected from the Glaxo registry file for contractile activity on the isolated guinea pig gallbladder (GPGB) identified a series of 1,5-benzodiazepines with peripheral cholecystokinin (CCK) receptor agonist activity. Agonis
- Aquino, Christopher J.,Armour, Duncan R.,Berman, Judd M.,Birkemo, Larry S.,Carr, Robin A. E.,Croom, Dallas K.,Dezube, Milana,Dougherty Jr., Robert W.,Ervin, Gregory N.,Grizzle, Mary K.,Head, Julie E.,Hirst, Gavin C.,James, Michael K.,Johnson, Michael F.,Miller, Laurence J.,Queen, Kennedy L.,Rimele, Thomas J.,Smith, David N.,Sugg, Elizabeth E.
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p. 562 - 569
(2007/10/03)
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