- Synthesis, characterization, and antibacterial activity of dibenzildithiocarbamate derivates and Ni(II)–Cu(II) coordination compounds
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In this work, the study of the synthesis methodology to obtain dibenzylamine derivates as intermediates for the formation of dithicarbamate ligands (DTC) and its coordination compounds was conducted. Four molecules derived from dibenzylamine were synthesized by two methodologies: classical (reflux) and microwave. From these amines, Four dithiocarbamate ligands (DTC): dibenzyldithiocarbamate, N-benzyl-1-(4-methoxyphenyl)dithiocarbamate, N-benzyl-1-(4-chlorophenyl)dithiocarbamate, and N-benzyl-1-(3-nitrophenyl)dithiocarbamate, and eight coordination complexes with general formula [M(DTC)2]nH2O (M= Cu(II) and Ni(II)) were obtained. All the compounds were characterized using different spectroscopic and thermal techniques such as Fourier-transform infrared spectroscopy (FT-IR), ultraviolet–visible spectroscopy (UV–VIS), proton and carbon-13 nuclear magnetic resonance (1H and 13C NMR), thermogravimetric analysis–differential scanning calorimetry (TGA-DSC). Additionally, it was possible to characterize two new crystalline phases of salts through single-crystal X-ray diffraction: dibenzyl ammonium nitrate and N-benzyl-1-(3-nitrophenyl)ammonium chloride. Additionally, microbial inhibition tests were conducted using the dibenzildithiocarbamate derivates. All DTC compounds showed important activity against Pseudomonas aeruginosa and Staphylococcus aureus but less sensitivity against Escherichia coli and Mycobacterium smegmatis. Among the coordination compounds, only [Cu(N-benzyl-1-(3-nitrophenyl)dithiocarbamate)2] presented a moderate activity against M. smegmatis mc2 155.
- Amaya-Flórez, Andres,Aranaga, Carlos,D'Vries, Richard F.,Ellena, Javier,Flórez-López, Edwin,Macías, Mario,Pastrana-Dávila, Andrea
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- Metal-free selective reduction of acid chlorides to aldehydes using 1-hydrosilatrane
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This work uses 1-hydrosilatrane – an accessible and easy-to-handle reducing reagent – to selectively reduce acid chlorides to aldehydes. This metal-free reduction proceeds rapidly at ambient temperature in the presence of N-methylpyrrolidine, efficiently producing aldehydes in up to 54% yield and with the balance largely remaining as starting material. No over-reduced alcohol product is observed.
- Adler, Marc J.,Azam, Fawwaz,Raveenthrarajan, David
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supporting information
(2021/10/29)
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- Cyclometalated Half-Sandwich Iridium(III) Complexes: Synthesis, Structure, and Diverse Catalytic Activity in Imine Synthesis Using Air as the Oxidant
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Four air-stable cyclometalated half-sandwich iridium complexes 1-4 with C,N-donor Schiff base ligands were prepared through C-H activation in moderate-to-good yields. These complexes have been well characterized, and their exact structure was elaborated on by single-crystal X-ray analysis. The iridium(III) complexes 1-4 showed good catalytic activity in the imine synthesis under open-flask conditions (air as the oxidant) from primary amine oxidative homocoupling, secondary amine dehydrogenation, and the cross-coupling reaction of amine and alcohol. Substituents bonded on the ligands of the iridium complexes displayed little effect on the catalytic efficiency. The stability and good catalytic efficiency of the iridium catalysts, mild reaction conditions, and substrate universality showed their potential application in industrial production.
- Li, Rong-Jian,Ling, Chun,Lv, Wen-Rui,Deng, Wei,Yao, Zi-Jian
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p. 5153 - 5162
(2021/05/04)
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- Nickel Complexes Bearing N,N,O-Tridentate Salicylaldiminato Ligand: Efficient Catalysts for Imines Formation via Dehydrogenative Coupling of Primary Alcohols with Amines
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Treatment of salicylaldiminato ligand L1H-L2H (L1H = 2,4-di-tert-butyl-6-((quinolin-8-ylimino)methyl)phenol; L2H = 2,4-di-tert-butyl-6-(((2-(diethylamino)ethyl)imino)methyl)phenol) with Ni(OAc)2·4H2O in refluxing ethanol afforded nickel complexes [(L1)Ni(OAc)] (1) and [(L2)Ni(OAc)] (2), respectively. Reaction of L3H (L3H = (2,4-di-tert-butyl-6-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenol)) with Ni(OAc)2·4H2O in the presence of excess triethylanmine gave the dual ligands coordinated nickel complex [(L2)2Ni] (3). Complexes 1-3 were well characterized by high-resolution mass spectrometry, infrared spectroscopy, elemental analysis, and X-ray diffraction analysis. All the three Ni(II) complexes exhibited efficient activity and good selectivity in the acceptorless dehydrogenative coupling of alcohols and amines to produce imines and diimines. The present protocol provides an atom-economical and sustainable route for the synthesis of various imine derivatives by employing an earth-abundant nickel salt and easily prepared salicylaldiminato ligands.
- Han, Zhangang,Hao, Zhiqiang,Lin, Jin,Lu, Guo-Liang,Zhang, Junhua,Zhang, Xiaoying
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p. 3843 - 3853
(2021/11/18)
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- Electrochemical, Iodine-Mediated α-CH Amination of Ketones by Umpolung of Silyl Enol Ethers
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The electrochemical, oxidative Umpolung reaction of silyl enol ethers utilizing simple iodide salts for the synthesis of α-amino ketones is described. The products were isolated in excellent yields of up to 100percent, and various functionalized starting materials were accepted in an undivided electrochemical cell design. Moreover, a sensitivity assessment to ensure an improved reproducibility of the reaction and cyclic voltammetry experiments were performed to postulate a plausible reaction mechanism on their basis.
- Strehl, Julia,Hilt, Gerhard
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supporting information
p. 5968 - 5972
(2020/08/12)
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- Efficient Co-Catalyzed Double Hydroboration of Nitriles: Application to One-Pot Conversion of Nitriles to Aldimines
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The commercially available and bench-stable Co(acac)2/dpephos system is employed as a precatalyst for selective and efficient room temperature hydroboration of organic nitriles with HBPin to produce a series of N,N-diborylamines [RN(BPin)2], which react in situ with aldehydes to give aldimines. Formation of aldimines from N,N-diborylamines does not require a dehydrating agent, is applicable to a wide range of N,N-diborylamine and aldehyde substrates and is highly chemoselective, being unaffected by various common functional groups, such as alkenes, alkynes, secondary amines, ketones, esters, amides, carboxylic acids, pyridines, nitriles, and nitro compounds. The overall transformation represents a synthetically valuable approach to aldimines from nitriles and can be performed in a sequential one-pot manner, tolerating ester, lactone, carboxamide and unactivated alkene functionalities.
- Gudun, Kristina A.,Slamova, Ainur,Hayrapetyan, Davit,Khalimon, Andrey Y.
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supporting information
p. 4963 - 4968
(2020/04/17)
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- Air-Stable Half-Sandwich Iridium Complexes as Aerobic Oxidation Catalysts for Imine Synthesis
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Several N,O-coordinate half-sandwich iridium complexes, 1-5, containing constrained bulky β-enaminoketonato ligands were prepared and clearly characterized. Single-crystal X-ray diffraction characterization of these complexes indicates that the iridium center adopts a distorted octahedral geometry. Complexes 1-5 showed good catalytic efficiency in the oxidative homocoupling of primary amines, dehydrogenation of secondary amines, and the oxidative cross-coupling of amines and alcohols, which furnished various types of imines in good yields and high selectivities using O2 as an oxidant under mild conditions. No distinctive substituent effects of the iridium catalysts were observed in these reactions. The diverse catalytic activity, broad substrate scope, mild reaction conditions, and high yields of the products made this catalytic system attractive in industrial processes.
- Deng, Wei,Fan, Xiao-Nan,Ou, Hui-Dan,Yao, Zi-Jian
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supporting information
(2020/04/02)
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- Activation of primary amines by copper(i)-based lewis acid promoters in the solventless synthesis of secondary propargylamines
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Primary amines are activated by copper(I)-based Lewis acid promoters in an A 3 -coupling one-pot solventless reaction with aldehydes and phenylacetylene for the synthesis of secondary propargylamines. The reaction is promoted by a CuSO 4 /NaI system, a practical precursor of the in situ generated effective CuI/I 2 system, that worked well, but only in a restricted number of examples. Substitution of I 2 with CeCl 3 ·7H 2 O in a one-pot two-step reaction provided good yields and a wider applicability, with the added value given by a safer procedure.
- Cimarelli, Cristina,Navazio, Federica,Rossi, Federico V.,Del Bello, Fabio,Marcantoni, Enrico
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p. 2387 - 2396
(2019/05/27)
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- Synthesis and characterization of Ni(II) complexes with functionalized dithiocarbamates: New single source precursors for nickel sulfide and nickel-iron sulfide nanoparticles
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Six Ni(II) complexes, bis(N-benzyl-N-substituted benzyldithiocarbamato-S,S′)nickel(II) (1–3), (N-benzyl-N-substituted benzyldithiocarbamato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II) (4–6), [Substituted benzyl=4-hydroxybenzyl (1, 4), 4-methoxybenzyl (2, 5), 4-chlorobenzyl (3, 6)] complexes have been synthesized and characterized by elemental analysis, IR, UV–Vis and NMR (1H and 13C) spectroscopy. Upfield shift of NCS2 carbon signals of heteroleptic complexes compared to homoleptic complexes supports the back bonding effect of triphenylphosphine. Structures of complexes 1, 4, 5 and 6 have been obtained by single crystal X-ray diffraction. The coordination geometry around nickel is a distorted square planar in all the complexes. Intramolecular Ni?H-C anagostic interaction is observed in 4. Various non-covalent interactions such as C-H?π(chelate), C-H?π and C-H?X (X = O and Cl) lead to supramolecular aggregation. [Ni(dbdtc)2] and [Ni(dbdtc)3][FeCl4] (dbdtc = N,N-dibenzyldithiocarbamate) were used to prepare monometallic sulfide (nickel sulfide), bimetallic sulfide (iron-nickel sulfide) nanoparticles. TEM images of nickel sulfide and iron-nickel sulfide reveal that the particles are oval shape and ultrafine (~5–10 nm), respectively.
- Sathiyaraj,Thirumaran,Ciattini, Samuele,Selvanayagam
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- α-Acyl-α-diazoacetates in Transition-Metal-Free β-Lactam Synthesis
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Thermally promoted reaction of α-acyl-α-diazoacetates with imines has been investigated. The transformation, earlier reported predominantly under transition metal catalyzed conditions, delivers α-alkoxycarbonyl-substituted β-lactams with outstanding diastereoselectivity. DFT calculations performed in order to evaluate energetically feasible reaction pathways revealed the intermediacy of 1,3-oxazin-4-one intermediates hitherto never implicated in the Staudinger synthesis of β-lactams.
- Synofzik, Judith,Dar'In, Dmitry,Novikov, Mikhail S.,Kantin, Grigory,Bakulina, Olga,Krasavin, Mikhail
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p. 12101 - 12110
(2019/10/02)
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- Acceptorless dehydrogenative construction of CN and CC bonds through catalytic aza-Wittig and Wittig reactions in the presence of an air-stable ruthenium pincer complex
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The construction of CN bonds was achieved by the dehydrogenative coupling of alcohol and azide via aza-Wittig type reaction. The reaction is catalyzed by an acridine-derived ruthenium pincer complex and does not use any oxidant. The present protocol offers a wide substrate scope, including aliphatic, aryl or heteroaryl alcohol/azides. This expeditious protocol was successfully applied to construct a CC bond directly from alcohol via dehydrogenative Wittig reaction. Furthermore, the synthesis of structurally important pyrrolo[1,4]benzodiazepine derivatives was also achieved by this methodology.
- Biswas, Nandita,Das, Kalicharan,Sardar, Bitan,Srimani, DIpankar
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p. 6501 - 6512
(2019/05/24)
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- Bi-functional catalyst of porous N-doped carbon with bimetallic FeCu for solvent-free resultant imines and hydrogenation of nitroarenes
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The efficient and stable catalyst applied to the transformation of amines into the corresponding imines and hydrogenation of nitroarenes under mild reaction conditions is reported. The catalytic performance of porous N-doped carbon with FeCu (FeCu@NPC) catalyst are tested by aromatic alcohol-based N-alkylated of amines with solvent-free and hydrogenation of nitroarenes via N2H4·H2O. The results proved that the yield of these two reactions are all over 99.9% under optimum condition. Moreover, the synergistic effect of the catalyst for N-alkylated reaction was investigated through the kinetic study. The catalyst can be easily separated from reaction system by an external magnetism, and can be recycled and reutilized for at least 4 runs with conversions are all over 75%. The study of the catalyst indicated that it was suitable for the reactions in industry. Hence, the catalysis process by the inexpensive metals-based catalyst is green and sustainable.
- Wang, Kaizhi,Gao, Wenbing,Jiang, Pengbo,Lan, Kai,Yang, Ming,Huang, Xiaokang,Ma, Lei,Niu, Fang,Li, Rong
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- Au nanoparticle-immobilized L-cysteine-paired porous ionic copolymer as an efficient catalyst for additive-free oxidative coupling of alcohols and amines
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Herein, an L-cysteine-paired ionic copolymer (DVB-[MimLcy]n) with mesoporosity was prepared by free radical copolymerization of divinylbenzene (DVB) and imidazolium ionic liquids (ILs), followed by anion-exchange with L-cysteine. Because of the rich functional groups of –NH2, –SH, and –COO– and the porous framework, the DVB-[MimLcy]3 was revealed to be an ideal stabilizer for metal nanoparticles (NPs). Highly uniform dispersed small Au NPs (2–3 nm) immobilized on DVB-[MimLcy]3 (Aua/DVB-[MimLcy]3) can act as an efficient heterogeneous catalyst for additive-free synthesis of imines through coupling of a broad range of alcohols and organic amines and can be easily recovered and steadily reused several times.
- Du, Shengyu,Zhang, Chenjun,Jiang, Yuchen,Jiang, Pingping,Leng, Yan
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- Dynamic Covalent Metathesis in the C=C/C=N Exchange between Knoevenagel Compounds and Imines
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Fast and reversible dynamic covalent C=C/C=N exchange takes place without catalyst in nonpolar solvents between barbiturate-derived Knoevenagel (Kn) compounds and imines. A detailed study of the reaction indicates that it proceeds by an associative organo-metathesis mechanism involving the formation of a four-membered ring azetidine intermediate by addition of the imine C=N group to the C=C bond of the Kn compound. This intermediate could be generated cleanly and stabilized at low temperature by condensation of the o,p-dinitrophenyl Kn derivative with the cyclic imine 1-azacyclohexene. It was characterized by extensive NMR and mass spectrometric studies. The process described represents a genuine dynamic covalent organo-metathesis through a four-membered ring adduct as intermediate. It paves the way for the exploration of a wide set of dynamic systems involving (strongly) polarized C=C bonds and various imines, extending also into covalent dynamic polymers and polymolecular assemblies.
- Gu, Ruirui,Flidrova, Karolina,Lehn, Jean-Marie
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supporting information
p. 5560 - 5568
(2018/05/01)
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- Selective aerobic oxidation of halides and amines with an inorganic-ligand supported zinc catalyst
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A practical, efficient and environmentally benign catalytic protocol for the oxidative cross-coupling reaction of halides with amines, oxidative self-coupling of amines and oxidation of halides was developed with inorganic-ligand supported ZnPOM (NH4)4[ZnMo6O18(OH)6] using molecular oxygen. This method mainly utilizes an inorganic polymolybdate ligand to support the Zn2+ ion, avoiding the use of complicated organic ligands.
- Wang, Jingjing,Zhai, Yongyan,Wang, Ying,Yu, Han,Zhao, Wenshu,Wei, Yongge
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p. 13323 - 13327
(2018/10/15)
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- Visible-Light-Driven Photocatalytic Oxidation of Organic Chlorides Using Air and an Inorganic-Ligand Supported Nickel-Catalyst Without Photosensitizers
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Engineering photoredox-triggered chemical transformation via visible light has been an emerging area in organic synthesis. However, most of the well-established photocatalysts are based upon either transition metal complexes involved with noble metals and organic ligands or photosensitive organic dyes, the development of pure inorganic molecular photocatalysts that could provide better stability and durability is greatly retarded. Herein we discover that the Anderson polyoxometalate (POM) Na4[NiMo6O18(OH)6] (1), which consists of pure inorganic framework built from a central NiII core supported by six MoVIO6 inorganic scaffold/ligands, can be used as a powerful photocatalyst. Upon irradiation with visible light (>400 nm), the compound can catalyze, in high efficiency, a wide range of reactions, including the oxidative cross-coupling reaction of chlorides with amines, as well as oxidation of chlorides using molecular oxygen, affording various imines, aldehydes, and ketones, respectively in high selectivity and good yields. Owing to the robust inorganic framework, this catalyst exhibits excellent stability during the catalysis and reusability with little loss of the catalytic activity, thus providing an alternative without use of complicated organic ligands and expensive noble metal-based photosensitizers.
- Yu, Han,Wang, Jingjing,Zhai, Yongyan,Zhang, Mengqi,Ru, Shi,Han, Sheng,Wei, Yongge
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p. 4274 - 4279
(2018/09/10)
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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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supporting information
p. 3180 - 3185
(2018/07/29)
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- Ru Nanoparticles-Loaded Covalent Organic Framework for Solvent-Free One-Pot Tandem Reactions in Air
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Condensation of benzene-1,3,5-tricarbohydrazide with benzene-1,4-dicarboxaldehyde generated a new covalent organic framework, COF-ASB (1), in which the organic units are held together via hydrazone linkage to form porous frameworks. COF-ASB (1) is highly crystalline and displays good chemical and thermal stability and is permanently porous. In addition, 1 can be an ideal support to load Ru nanoparticles (Ru NPs) to generate Ru@COF-ASB (2). The obtained composite material is able to highly promote one-pot tandem synthesis of imine products from benzyl alcohols and corresponding amines under solvent-free conditions in air.
- Chen, Gong-Jun,Li, Xiao-Bo,Zhao, Chen-Chen,Ma, Hui-Chao,Kan, Jing-Lan,Xin, Yu-Bin,Chen, Cheng-Xia,Dong, Yu-Bin
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supporting information
p. 2678 - 2685
(2018/03/13)
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- One-pot synthesis of alternating peptides exploiting a new polymerization technique based on Ugi's 4CC reaction
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We developed a one-pot synthetic technique for alternating peptides. Central to this technique is a new, catalyst-free polymerization based on Ugi's 4CC reaction. The treatment of imines with the ambident molecules bearing both an isocyanide and a carboxylic acid afforded alternating peptides.
- Koyama, Yasuhito,Gudeangadi, Prashant G.
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supporting information
p. 3846 - 3849
(2017/04/04)
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- A Metal-Free Approach to 1,2-Diamines via Visible Light-Driven Reductive Coupling of Imines with Perylene as a Photoredox Catalyst
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A simple, metal-free, and versatile approach to 1,2-diamines has been developed based on reductive coupling reactions of various imines, where perylene, an aromatic hydrocarbon, was used as a photoredox catalyst under visible light irradiation using a white light-emitting diode. The use of 1 mol % perylene enabled almost complete conversion of the imines, leading to the formation of their corresponding 1,2-diamines, which were isolated in good yields. The ratios between dl and meso diamines ranged from 31:69 to 82:18 depending on the substituents of the imines.
- Okamoto, Shusuke,Ariki, Risako,Tsujioka, Hiroki,Sudo, Atsushi
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p. 9731 - 9736
(2017/09/23)
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- A facile synthesis of stable β-amino-N-/O-hemiacetals through a catalyst-free three-component Mannich-type reaction
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A practical, straightforward and one-step procedure for the synthesis of novel and stable β-amino-N-/O-hemiacetals (i.e. γ-aminoalcohols) is provided. The title compounds were obtained in good to excellent yields through an uncatalyzed three-component reaction by treatment of secondary amines with polyformaldehyde and electron-rich alkenes in acetonitrile as solvent at ambient temperature. The reactions proceeded with the formation of iminium ions, through a Mannich-type reaction, as the key intermediates for the generation of the target products. Single crystal X-ray analysis of derivative 4l confirmed unequivocally the structure and stability of the obtained compounds.
- Abonia, Rodrigo,Castillo, Juan C.,Garay, Alexander,Insuasty, Braulio,Quiroga, Jairo,Nogueras, Manuel,Cobo, Justo,D'Vries, Richard
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supporting information
p. 1490 - 1494
(2017/03/23)
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- Beyond the five and six: Evaluation of seven-membered cyclic anhydrides in the castagnoli-cushman reaction
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The Castagnoli-Cushman reaction with benzo[d]- oxepine-2,4(1H,5H)-dione as an anhydride component allowed for preparation of 2,3-disubstituted 4-oxo-2,3,4,5-tetrahydro-1H-benzo[d]- azepine-1-carboxylic acids in 21-75% yields and with good trans diastereoselectivity. The method worked with imines generated from aromatic or a-branched aliphatic aldehydes and is amenable for both parallel synthesis and scale-up. The procedure for epimerization of the resulting trans-disubstituted tetrahydrobenzo[d]azepines to their cis isomers was also developed.
- Adamovskyi, Mykhailo I.,Ryabukhin, Sergey V.,Sibgatulin, Dmitriy A.,Rusanov, Eduard,Grygorenko, Oleksandr O.
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supporting information
p. 130 - 133
(2017/09/08)
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- Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines
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Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH4)n[MMo6O18(OH)6] (M=Cu2+; Fe3+; Co3+; Ni2+; Zn2+, n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six MoVI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis.
- Yu, Han,Zhai, Yongyan,Dai, Guoyong,Ru, Shi,Han, Sheng,Wei, Yongge
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supporting information
p. 13883 - 13887
(2017/10/13)
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- Dual Heterogeneous Catalyst Pd-Au@Mn(II)-MOF for One-Pot Tandem Synthesis of Imines from Alcohols and Amines
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A new Mn(II) metal-organic framework (MOF) 1 was synthesized by the combination of 4,4,4-trifluoro-1-(4-(pyridin-4-yl)phenyl)butane-1,3-dione (L) and Mn(OAc)2 in solution. 1 features a threefold-interpenetrating NbO net containing honeycomb-like channels, in which the opposite Mn(II)···Mn(II) distance is 23.5075(10) ?. Furthermore, 1 can be an ideal platform to support Pd-Au bimetallic alloy nanoparticles to generate a composite catalytic system of Pd-Au@Mn(II)-MOF (2). 2 can be a highly active bifunctional heterogeneous catalyst for the one-pot tandem synthesis of imines from benzyl alcohols and anilines and from benzyl alcohols and benzylamines.
- Chen, Gong-Jun,Ma, Hui-Chao,Xin, Wen-Ling,Li, Xiao-Bo,Jin, Fa-Zheng,Wang, Jing-Si,Liu, Ming-Yang,Dong, Yu-Bin
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supporting information
p. 654 - 660
(2017/01/13)
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- Aerobic oxidative coupling of alcohols and amines towards imine formation by a dicopper(I,I) catalyst
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A dicopper(I,I) complex [Cu2(L1) (Cl)2] (1), bearing a Cu2Cl2 core spanned by a naphthyridine–diimine ligand is synthesized by the treatment of CuCl with 2,7–bis(N–mesitylmethylimino)–1,8–naphthyridine (L1). The catalytic efficacy of 1 is assessed for aerobic oxidative synthesis of imines from alcohols and amines. The title complex is found to be an excellent catalyst for a wide variety of alcohols and amines. Kinetic experiments revealed the involvement of both copper ions in the aerobic oxidation process. The general utility of naphthyridine based ligands to favour a possible bimetallic pathway for a catalytic reaction is demonstrated here.
- Dutta, Indranil,De, Subhabrata,Yadav, Sudhir,Mondol, Ranajit,Bera, Jitendra K.
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p. 117 - 124
(2017/09/30)
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- Method for synthesizing imine through cross-coupling of hydroxylation phenanthroline copper complex/O2 catalytic oxidation alcohol and amine
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The invention discloses a method for synthesizing imine through cross-coupling of hydroxylation phenanthroline copper complex/O2 catalytic oxidation alcohol and amine. According to the method, an economical and cheap hydroxylation phenanthroline copper complex is selected as a catalyst, green O2 is selected as an oxidizing agent, cross-coupling of alcohol and amine is realized under the condition of normal temperature, alkali and an expensive free radical of nitroxide is prevented from being used, and a series of imine compounds are successfully prepared. The method provided by the invention is high in reaction selectivity and relatively wide in a substrate application range, and has a great industrial application potential.
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Paragraph 0017; 0020; 0021
(2017/12/02)
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- MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS
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The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di- lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.
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Paragraph 00277-00278
(2017/09/05)
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- A one-pot synthesis of highly substituted tetrahydropyridines from N-benzylidenemethanamines, dialkyl acetylenedicarboxylates and benzylidenemalononitriles
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A simple and efficient synthesis of highly substituted tetrahydropyridines has been develope using a one-pot, two step reactions. The synthesis of a series of N-benzylidenemethanamine from benzylamines and benzaldehydes in the presence of acetic acid, followed by cyclizatio with dialkyl acetylenedicarboxylates and benzylidenemalononitriles, gave the correspondin tetrahydropyridines in good yields.
- Mehrabi, Hossein,Mohebbi, Ahmad
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- Effect of functionlization of N, N -dibenzyldithiocarbamate: Synthesis, spectral and structural studies on bis(N -benzyl- N -(4-methoxybenzyl)dithiocarbamato-S,S′)zinc(II) and bis(N -benzyl- N -(4-cholrobenzyl)dithiocarbamato-S,S′)cadmium(II) and their use for the preparation of MS (M = Zn, Cd)
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Bis(N-benzyl-N-(4-methoxybenzyl)dithiocarbamato-S,S′)zinc(II) (1) and bis(N-benzyl-N-(4-chlorobenzyl)dithiocarbamato-S,S′)cadmium(II) (2) have been prepared and characterized by elemental analysis, IR and NMR (1H and 13C) spectroscopy and single-crystal X-ray analysis. Complexes 1 and 2 exist as monomer and dimer, respectively. Crystal structures of 1 and 2 confirm the presence of four coordinated zinc in a distorted tetrahedral arrangement and five coordinated cadmium in a distorted square pyramid arrangement, respectively. Both the complexes are further stabilized by various interactions such as C-H···S, C-H···N, C-H···O and C-H···π (chelate). C-H···O interaction leads to the formation of dimer in complex 1. In complex 2, C-H···π (chelate) interaction runs in opposite directions which results in the polymeric chain. ZnS and CdS have been prepared from 1 and 2, respectively, and characterized by powder X-ray diffraction, SEM, UV-Vis and fluorescence spectroscopy. The X-ray diffraction pattern confirms the wurtzite phase of as-prepared ZnS and CdS.
- Gomathi, Govindaraju,Sathiyaraj, Ethiraj,Thirumaran, Subbiah,Ciattini, Samuele
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- Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride MnIand FeIIPNP Pincer Complexes
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Herein, we describe an efficient coupling of alcohols and amines catalyzed by well-defined isoelectronic hydride MnIand FeIIcomplexes, which are stabilized by a PNP ligand based on the 2,6-diaminopyridine scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant non-precious metal catalysts, and is based on the acceptorless alcohol dehydrogenation concept. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted in good to excellent isolated yields. Although in the case of Mn selectively imines were obtained, with Fe—exclusively monoalkylated amines were formed. These reactions proceed under base-free conditions and required the addition of molecular sieves.
- Mastalir, Matthias,Glatz, Mathias,Gorgas, Nikolaus,St?ger, Berthold,Pittenauer, Ernst,Allmaier, Günter,Veiros, Luis F.,Kirchner, Karl
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supporting information
p. 12316 - 12320
(2016/08/24)
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- Manganese-Catalyzed Environmentally Benign Dehydrogenative Coupling of Alcohols and Amines to Form Aldimines and H2: A Catalytic and Mechanistic Study
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The catalytic dehydrogenative coupling of alcohols and amines to form aldimines represents an environmentally benign methodology in organic chemistry. This has been accomplished in recent years mainly with precious-metal-based catalysts. We present the dehydrogenative coupling of alcohols and amines to form imines and H2 that is catalyzed, for the first time, by a complex of the earth-abundant Mn. Detailed mechanistic study was carried out with the aid of NMR spectroscopy, intermediate isolation, and X-ray analysis.
- Mukherjee, Arup,Nerush, Alexander,Leitus, Gregory,Shimon, Linda J. W.,Ben David, Yehoshoa,Espinosa Jalapa, Noel Angel,Milstein, David
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supporting information
p. 4298 - 4301
(2016/05/09)
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- Deep eutectic solvent catalyzed eco-friendly synthesis of imines and hydrobenzamides
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The urea-choline chloride-based deep eutectic solvent was found to be an efficient catalyst and reaction media for the additive-free synthesis of imines (Schiff bases) and hydrobenzamides by the reaction of aldehydes with amines and ammonia in good to high yields. Outstanding features of this protocol were the general and atom-economical reaction, absence of external catalysts and additives, simple workup, and availability and recycling of urea-choline chloride as a green solvent. Graphical abstract: (Chemical Equation Presented).
- Azizi, Najmedin,Edrisi, Mahtab
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p. 1695 - 1698
(2015/09/21)
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- Palladium-catalyzed [4 + 2] cycloaddition of aldimines and 1,4-dipolar equivalents via amphiphilic allylation
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The combination of Pd catalyst and diethylzinc with triethylborane promotes the amphiphilic allylation of aldimines with 2,3-bismethylenebutane-1,4-diol derivatives to serve as bis-allylic zwitterion species to form 3,4-bismethylenepiperidines via a formal [4 + 2] cycloaddition reaction. 3,4-Bismethylenepiperidine rings are applicable for the synthesis of isoquinoline derivatives via the Diels-Alder reaction followed by an oxidation reaction with DDQ.
- Hirata, Goki,Yamada, Naoshi,Sanada, Shohei,Onodera, Gen,Kimura, Masanari
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supporting information
p. 600 - 603
(2015/03/04)
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- New Heterocyclic Product Space for the Castagnoli-Cushman Three-Component Reaction
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Significant expansion of heterocyclic product space accessible by the Castagnoli-Cushman reaction (CCR) has been achieved via the use of glutaric anhydride analogues containing endocyclic substitutions with oxygen, nitrogen, and sulfur. Incorporation of these heteroatoms in the anhydride's backbone results in enhanced reactivity and generally lower temperatures that are required for the reactions to go to completion. These findings are particularly significant in light of the CCR recently recognized as an efficient tool for lead-oriented synthesis.
- Dar'In, Dmitry,Bakulina, Olga,Chizhova, Maria,Krasavin, Mikhail
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supporting information
p. 3930 - 3933
(2015/08/18)
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- Lanthanide coordination polymer constructed from 2,2′-bipyridyl-4,4′-dicarboxylic acid: Structure, catalysis and fluorescence
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Two new isostructural lanthanide coordination polymers (Ln-CPs) [Ln2(bpdc)3(DMF)2] (Ln = Tb for 1, Eu for 2) with two kinds of one-dimensional channels along the a axis, were synthesized by 2,2′-bipyridyl-4,4′-dicarboxylic acid (H2bpdc) under solvothermal conditions. With exposed Lewis acid Ln3+ centers, 1 as a heterogeneous catalyst shows good catalytic reactivity and selectivity for the Strecker reaction affording medium to excellent conversion yields. Luminescent studies illustrate that 1 and 2 show intensive green and red luminescence triggered by efficient antenna effect of ligands under UV light, respectively. Moreover, 1 exhibits sensitive fluorescent response to Cu2+ in DMF solution.
- Wang, Shengyan,Xu, Jianing,Zheng, Jifu,Chen, Xiaodong,Shan, Liang,Gao, Lijuan,Wang, Li,Yu, Miao,Fan, Yong
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supporting information
p. 81 - 86
(2015/09/15)
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- Factors influencing the regioselectivity of the oxidation of asymmetric secondary amines with singlet oxygen
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Aerobic amine oxidation is an attractive and elegant process for the α functionalization of amines. However, there are still several mechanistic uncertainties, particularly the factors governing the regioselectivity of the oxidation of asymmetric secondary amines and the oxidation rates of mixed primary amines. Herein, it is reported that singlet-oxygen-mediated oxidation of 1° and 2° amines is sensitive to the strength of the α-C-H bond and steric factors. Estimation of the relative bond dissociation energy by natural bond order analysis or by means of one-bond C-H coupling constants allowed the regioselectivity of secondary amine oxidations to be explained and predicted. In addition, the findings were utilized to synthesize highly regioselective substrates and perform selective amine cross-couplings to produce imines.
- Ushakov, Dmitry B.,Plutschack, Matthew B.,Gilmore, Kerry,Seeberger, Peter H.
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supporting information
p. 6528 - 6534
(2015/04/22)
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- Pseudorotaxane orientational stereoisomerism driven by π-electron density
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Pseudo[2]rotaxane orientational isomers were formed in a stereocontrolled way by exploiting the electron-withdrawing (EW) or electron-donating (ED) effects of para-substituted dibenzylammonium axles threaded through the π-electron rich calixarene cavity, which allow the fine tuning of the weak π-π interactions.
- Gaeta, Carmine,Talotta, Carmen,Neri, Placido
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supporting information
p. 9917 - 9920
(2014/08/18)
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- Ti-mediated intramolecular cyclopropanation of N-alkenyl thioamides: Scope and mechanistic study
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Although thioamides generally undergo a reductive alkylation process when they are treated with a Grignard reagent in the presence of Ti(OiPr) 4, substrates fitted with a but-3-enyl substitution at the nitrogen atom are shown to be converted into bicyclic aminocyclopropanes. These reactions are compared with the similar cyclisations of the corresponding carboxylic amide substrates. A mechanistic study is provided. Coincidently, new reagent systems are identified for the mediation of the same transformation.
- Hermant, Fabien,Nicolas, Emmanuel,Six, Yvan
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supporting information
p. 3924 - 3930
(2014/06/09)
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- Semi-catalytic reduction of secondary amides to imines and aldehydes
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Secondary amides can be reduced by silane HSiMe2Ph into imines and aldehydes by a two-stage process involving prior conversion of amides into iminoyl chlorides followed by catalytic reduction mediated by the ruthenium complex [Cp(i-Pr3P)Ru(NCCH3)2]PF6 (1). Alkyl and aryl amides bearing halogen, ketone, and ester groups were converted with moderate to good yields under mild reaction conditions to the corresponding imines and aldehydes. This procedure does not work for substrates bearing the nitro-group and fails for heteroaromatic amides. In the case of cyano substituted amides, the cyano group is reduced to imine.
- Lee, Sun-Hwa,Nikonov, Georgii I.
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supporting information
p. 8888 - 8893
(2014/06/09)
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- METHOD FOR THE CATALYTIC REDUCTION OF ACID CHLORIDES AND IMIDOYL CHLORIDES
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The present application relates to methods for the catalytic reduction of acid chlorides and/or imidoyl chlorides. The methods comprise reacting the acid chloride or imidoyl chloride with a silane reducing agent in the presence of a catalyst such as [Cp(Pri3P)Ru(NCMe)2]+[PF6]?.
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Paragraph 0176
(2014/08/19)
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- Alcohol amination with ammonia catalyzed by an acridine-based ruthenium pincer complex: A mechanistic study
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The mechanistic course of the amination of alcohols with ammonia catalyzed by a structurally modified congener of Milstein's well-defined acridine-based PNP-pincer Ru complex has been investigated both experimentally and by DFT calculations. Several key Ru intermediates have been isolated and characterized. The detailed analysis of a series of possible catalytic pathways (e.g., with and without metal-ligand cooperation, inner- and outer-sphere mechanisms) leads us to conclude that the most favorable pathway for this catalyst does not require metal-ligand cooperation.
- Ye, Xuan,Plessow, Philipp N.,Brinks, Marion K.,Schelwies, Mathias,Schaub, Thomas,Rominger, Frank,Paciello, Rocco,Limbach, Michael,Hofmann, Peter
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supporting information
p. 5923 - 5929
(2014/05/20)
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- Catalytic activity of MCM-41 and Al grafted MCM-41 for oxidative self and cross coupling of amines
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The catalytic activity of MCM-41 mesoporous silica (MS) and Al grafted MCM-41 (Al-MS) with varied amount of Al were studied for oxidative self and cross coupling of benzyl amines to imines. The role of Al, its amount, acidity of the catalyst, effect of reaction conditions (especially presence of solvent and excess air) and amines nature on the oxidative coupling reactions were investigated. Surface OH groups play an effective role in amine activation by hydrogen bonding, whereas the acid sites generated by incorporation of optimum amount of Al further improve the activity. The Al in optimum amount (Si/Al: 20) showed good catalytic activity in self coupling of benzyl amine as compared to MS and Al-MS with high Al loading. A suitable polar solvent and presence of excess air significantly promote the activity of MS and Al-MS for amine coupling reactions. The MS without Al was also found to be efficient catalyst for oxidative self and cross coupling of amines. The presence of Al in Al-MS (in optimum amount, i.e., Si/Al: 20) made the self coupling of benzyl amine faster than MS, whereas the cross coupling reactions with Al-MS were observed to be slightly slower than MS, which is probably due to competitive adsorption of amine substrate and amine nucleophile over acidic sites. The activity of MS and Al-MS catalysts for self and cross coupling reactions was also dependent of the amines nature (basicity and nucleophilicity).
- Tayade, Kamlesh N.,Mishra, Manish
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p. 114 - 125
(2014/01/06)
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- Selective aerobic oxidation of alcohols to aldehydes, carboxylic acids, and imines catalyzed by a Ag-NHC complex
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Silver NHC catalysts have been developed for the selective oxidation of alcohols to aldehydes or carboxylic acids in the presence of BnMe3NOH or KOH under dry air. The aerobic oxidation conditions are mild, and the yield is excellent. Further tandem catalysis enables the one-pot synthesis of imines in excellent yield. Only 0.1 mol % of the catalyst is required.
- Han, Lei,Xing, Ping,Jiang, Biao
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supporting information
p. 3428 - 3431
(2014/07/21)
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- Morphology-tuned exceptional catalytic activity of porous-polymer-supported Mn3O4 in aerobic sp3 C-H bond oxidation of aromatic hydrocarbons and alcohols
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Mn3O4 nanomaterials with different morphologies (sphere, nanowire, and octahedron) embedded into functionalized nanoporous polymers were developed by a facile one-pot solvothermal technique at different temperatures. These Mn3O4-based hybrid materials could behave as heterogeneous nanocatalysts to perform sp3 C-H bond oxidation of aromatic hydrocarbons and alcohols with molecular oxygen as an economic oxidant. Catalytic activity could be effectively tuned by changing the morphology of incorporated Mn3O4 in nanoporous polymer. These Mn3O4-based hybrid materials exhibited remarkable catalytic performance for sp3 C-H bond oxidation as compared with bare Mn3O4 nanoparticles. Mn3O4 with octahedral morphology in nanoporous polymer exhibited the highest catalytic activity on account of its more exposed crystallographic planes and edges. These Mn3O4-based nanocatalysts could be recycled and reused for consecutive catalytic cycles without a significant loss of catalytic activity. Exceptional crystal facets: Nanoporous-polymer-supported Mn3O4 nanocatalysts (Mn@DVTA, DVTA=divinyltriallyl) with different morphologies are developed to catalyze aerobic sp3 C-H bond oxidation of aromatic hydrocarbons and alcohols. Among the different nanocatalysts, those with octahedral crystallite morphology exhibit outstanding catalytic performance.
- Mondal, John,Borah, Parijat,Sreejith, Sivaramapanicker,Nguyen, Kim Truc,Han, Xiguang,Ma, Xing,Zhao, Yanli
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p. 3518 - 3529
(2015/04/16)
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- Metal-Ligand cooperation on a diruthenium platform: Selective imine formation through acceptorless dehydrogenative coupling of alcohols with amines
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Metal-metal singly-bonded diruthenium complexes, bridged by naphthyridine-functionalized N-heterocyclic carbene (NHC) ligands featuring a hydroxy appendage on the naphthyridine unit, are obtained in a single-pot reaction of [Ru2(CH3COO)2(CO)4] with 1-benzyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (BIN-HBr) or 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazolium bromide (PIN-HBr), TlBF4, and substituted benzaldehyde containing an electron-withdrawing group. The modified NHC-naphthyridine-hydroxy ligand spans the diruthenium unit in which the NHC carbon and hydroxy oxygen occupy the axial sites. All the synthesized compounds catalyze acceptorless dehydrogenation of alcohols to the corresponding aldehydes in the presence of a catalytic amount of weak base 1,4-diazabicyclo[2.2.2]octane (DABCO). Further, acceptorless dehydrogenative coupling (ADHC) of the alcohol with amines affords the corresponding imine as the sole product. The substrate scope is examined with 1 (BIN, p-nitrobenzaldehyde). A similar complex [Ru2(CO) 4(CH3COO)(3-PhBIN)][Br], that is devoid of a hydroxy arm, is significantly less effective for the same reaction. Neutral complex 1 a, obtained by deprotonation of the hydroxy arm in 1, is found to be active for the ADHC of alcohols and amines under base-free conditions. A combination of control experiments, deuterium labeling, kinetic Hammett studies, and DFT calculations support metal-hydroxyl/hydroxide and metal-metal cooperation for alcohol activation and dehydrogenation. The bridging acetate plays a crucial role in allowing β-hydride elimination to occur. The ligand architecture on the diruthenium core causes rapid aldehyde extrusion from the metal coordination sphere, which is responsible for exclusive imine formation. Ligand lends a hand: Metal-hydroxy/hydroxide and metal-metal cooperation is demonstrated for acceptorless dehydrogenation of alcohols to give aldehydes. The ligand architecture ensures rapid extrusion of the aldehyde from the metal core, resulting in the formation of the corresponding imine as the sole coupled product with amines (see scheme; DABCO=1,4-diazabicyclo[2.2.2]octane).
- Saha, Biswajit,Wahidurrahaman,Daw, Prosenjit,Sengupta, Gargi,Bera, Jitendra K.
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p. 6542 - 6551
(2014/06/09)
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- Substituted 4-Oxo-1,2,3,4-tetrahydroquinoline-3-carboxylic esters by a tandem imine addition-SNAr reaction
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A tandem imine addition-SNAr annulation reaction has been developed as a new approach to the synthesis of 4-oxo-1,2,3,4- tetrahydroquinoline-3-carboxylic esters. A series of these structures has been generated by reacting selected imines with tert-butyl 2-fluoro-5- nitrobenzoylacetate. Structural variations in the final products are accomplished by changing the substituents on the imine and the alkyl group of the ester. The title compounds are isolated as their enols in 55-97% yield without the need for added base or catalysts. The synthesis of the starting materials as well as mechanistic studies and further synthetic conversions of the products are presented.
- Bunce, Richard A.,Schammerhorn, James E.,Sigle, Jessica
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p. 373 - 380
(2013/06/04)
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- Ugi four-component reaction of alcohols: Stoichiometric and catalytic oxidation/MCR sequences
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A new, simple, and efficient procedure for the one-pot Ugi four-component reaction of alcohols instead of aldehydes is described. Using a stoichiometric amount of IBX or only 1-2% of sodium 2-iodobenzenesulfonate in the presence of Oxone, a wide range of primary alcohols were oxidized to the aldehyde that were directly engaged in the Ugi four-component reaction to afford α-acetamidoamides in good to excellent yields.
- Drouet, Fleur,Masson, Géraldine,Zhu, Jieping
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supporting information
p. 2854 - 2857
(2013/07/26)
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- Cobalt-catalyzed acceptorless alcohol dehydrogenation: Synthesis of imines from alcohols and amines
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A cobalt catalyst has been developed for the acceptorless dehydrogenation of alcohols and applied to synthesize imines from alcohols and amines. Deuterium labeling studies suggest that the reaction proceeds by an initial reversible alcohol dehydrogenation step involving a cobalt hydride intermediate.
- Zhang, Guoqi,Hanson, Susan K.
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supporting information
p. 650 - 653
(2013/04/11)
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- Synthesis of α, α-dideutero-β-amino esters
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A straight forward entry to α, α-dideutero-β-amino esters starting from the corresponding imines and deuterated acetonitrile has been developed involving a two-step process.
- Chandrasekhar,Pendke, Mrunal,Muththe, Chandrashekar,Akondi, Srirama Murthy,Mainkar, Prathama S.
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experimental part
p. 1292 - 1295
(2012/03/27)
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- Coupling of two multistep catalytic cycles for the one-pot synthesis of propargylamines from alcohols and primary amines on a nanoparticulated gold catalyst
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A one-pot reaction was performed with a nanoparticulated gold catalyst. A secondary amine is formed through N-monoalkylation of a primary amine with an alcohol by a borrowing hydrogen methodology in a three-step reaction. The secondary amine formed enters into a second A3-coupling cycle to give propargylamines. The multistep reaction requires a gold species formed and stabilized on a ceria surface. Copyright
- Corma, Avelino,Navas, Javier,Sabater, Maria J.
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p. 14150 - 14156
(2013/01/15)
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