- Preparation and Coordination Properties Including Catalytic Activities of a Bulky 2-Methyl-3-thioxo-1,3-diphosphapropene
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(Matrix presented) 2-Methyl-3,3-diphenyl-3-thioxo-1-(2,4,6-tri-tert- butylphenyl)-1,3-diphosphapropene, which bears a P=C-P=S skeleton, was prepared and used as a ligand of transition-metal complexes. The palladium complexes containing the ligated 3-thioxo-1,3-diphophapropene were stable and used for catalytic reactions such as cross-couplings and direct conversion of allyl alcohol to allylaniline.
- Liang, Hongze,Ito, Shigekazu,Yoshifuji, Masaaki
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- Heterobimetallic Eu(iii)/Pt(ii) single-chain nanoparticles: a path to enlighten catalytic reactions
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We introduce the formation and characterization of heterometallic single-chain nanoparticles entailing both catalytic and luminescent properties. A terpolymer containing two divergent ligand moieties, phosphines and phosphine oxides, is synthesized and intramolecularly folded into nanoparticlesviaa selective metal complexation of Pt(ii) and Eu(iii). The formation of heterometallic Eu(iii)/Pt(ii) nanoparticles is evidenced by size exclusion chromatography, multinuclear NMR (1H,31P{1H},19F,195Pt) as well as diffusion-ordered NMR and IR spectroscopy. Critically, we demonstrate the activity of the SCNPs as a homogeneous and luminescent catalytic system in the amination reaction of allyl alcohol.
- Barner-Kowollik, Christopher,Kn?fel, Nicolai D.,Kulendran, Bragavie,Roesky, Peter W.,Rothfuss, Hannah,Tzvetkova, Pavleta
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- Copper-Catalyzed Allylation of Amines with Cyclopropyldiphenylsulfonium Trifluoromethanesulfonate
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Cyclopropyldiphenylsulfonium salt, a famous ylide precursor previously extensively employed in the preparation of cyclic compounds, has been successfully utilized as an efficient allylation reagent in this work. The copper-catalyzed reactions of cyclopropyldiphenylsulfonium trifluoromethanesulfonate with amines in the presence of an appropriate ligand provided the N-allylated products in good yields. Aliphatic/ aromatic amines and primary/secondary amines were all converted under mild reaction conditions. This protocol was also applicable to N-functionalization of drug molecules, supplying the corresponding N-allylated compounds in satisfactory yields. The reaction, which showed good functional group tolerance with a wide range of substrates and excellent chemoselectivity, offers an interesting method for the synthesis of N-allyl amines.
- Ma, Yu,Tian, Ze-Yu,Zhang, Cheng-Pan,Zheng, Shuang-Yang
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- Copper(i)-catalysed intramolecular hydroarylation-redox cross-dehydrogenative coupling ofN-propargylanilines with phosphites
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Intramolecular hydroarylation-redox cross-dehydrogenative coupling ofN-propargylanilines with phosphite diesters proceeded in the presence of Cu(i)-catalysts (20 mol%) to selectively give 2-phosphono-1,2,3,4-tetrahydroquinolines in good yields with 100% atomic utilization. P-H and two C-H bonds are activated at once and these hydrogen atoms are trapped by a propargylic triple bond in the molecule.
- Li, Guangzhe,Yu, Guo,Wang, Chengdong,Morita, Taiki,Zhang, Xuhai,Nakamura, Hiroyuki
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supporting information
p. 113 - 116
(2021/12/29)
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- Regioselective Radical Arene Amination for the Concise Synthesis ofortho-Phenylenediamines
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The formation of arene C-N bonds directly from C-H bonds is of great importance and there has been rapid recent development of methods for achieving this through radical mechanisms, often involving reactiveN-centered radicals. A major challenge associated with these advances is that of regiocontrol, with mixtures of regioisomeric products obtained in most protocols, limiting broader utility. We have designed a system that utilizes attractive noncovalent interactions between an anionic substrate and an incoming radical cation in order to guide the latter to the areneorthoposition. The anionic substrate takes the form of a sulfamate-protected aniline and telescoped cleavage of the sulfamate group after amination leads directly toortho-phenylenediamines, key building blocks for a range of medicinally relevant diazoles. Our method can deliver both free amines and monoalkyl amines allowing access to unsymmetrical, selectively monoalkylated benzimidazoles and benzotriazoles. As well as providing concise access to valuableortho-phenylenediamines, this work demonstrates the potential for utilizing noncovalent interactions to control positional selectivity in radical reactions.
- Gillespie, James E.,Morrill, Charlotte,Phipps, Robert J.
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supporting information
p. 9355 - 9360
(2021/07/19)
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- Fused ring compound and preparation method thereof
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The invention provides a fused ring compound and a preparation method thereof. In the method, precursor compounds A and B prepared under the conditions of triethylamine as a base, DMF as a solvent andpalladium acetate and triphenylphosphine as a catalyst react to generate a series of new fused ring compounds with a unique stereoselectivity. Compared with the conventional fused ring compound, thefused ring compound prepared by the invention has a more complicated structure, a mild reaction condition and a high reaction yield. The fused ring compound also shows a broader prospect of use in chemical production and clinical medicine.
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Paragraph 0052; 0056-0057
(2021/09/21)
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- Nickel-Catalyzed Aminofluoroalkylation of Alkenes: Access to Difluoroalkylated N-Containing Heterocyclic Compounds
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A nickel-catalyzed aminofluoroalkylative cyclization of unactive alkenes with iododifluoromethyl ketones was developed to construct versatile difluoroalkylated Nitrogen-containing heterocycles including aziridines, pyrrolidines and piperidines in moderate to high yields. This method features a broad substrate scope and has been demonstrated on gram scale.
- Fu, Xiaoyi,Sun, Yijie,Wu, Fanhong,Wu, Jingjing,Zhang, Tianyu
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supporting information
(2021/12/03)
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- Chitosan nanoparticles functionalized poly-2-hydroxyaniline supported CuO nanoparticles: An efficient heterogeneous and recyclable nanocatalyst for N-arylation of amines with phenylboronic acid at ambient temperature
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The present study aims to prepare an effective and eco-friendly nanocatalyst for the Chan–Lam coupling reaction of phenylboronic acid and amine in aerobic conditions. For this purpose, chitosan was extracted from shrimp shells waste by demineralization, deproteinization, and deacetylation processes and then converted to chitosan nanoparticles (CSN) by the ionic gelation with tripolyphosphate anions. Afterward, poly-2-hydroxyaniline (P2-HA) was grafted to chitosan nanoparticles (NPs) to employ as the support for CuO NPs. Characterization of the nanocatalyst was done using Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), mapping, energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The CuO NPs were identified in the spherical shape with an average size of 17 nm. The prepared nanocatalyst exhibited excellent catalytic performance with a high turnover number (TON) and turnover frequency (TOF) for the Chan–Lam coupling reaction of phenyl boronic acid and amines with different electronic properties. The prepared catalyst could be readily recovered and reused for at least five runs without any noticeable change in structure and catalytic performance. Chitosan (CS) was prepared via demineralization, deproteinization, and deacetylation of shrimp shell and chitosan nanoparticles (CSN) were prepared via ionic gelation process. Polymerization of 2-HA on the CSN surface was done to increase functional groups and create active sites for CuO NPs attachments. CuO NPs-P2-HA-CSN nanocomposite has been shown high efficiently for the Chan–Lam coupling reaction.
- Seyedi, Neda,Zahedifar, Mahboobeh
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- Synthesis of functionalized indoles via palladium-catalyzed cyclization of N-(2-allylphenyl) benzamide: A method for synthesis of indomethacin precursor
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We developed an efficient method for synthesis of substituted N-benzoylindole via Pd(II)-catalyzed C-H functionalization of substituted N-(2-allylphenyl)benzamide. The reaction showed a broad substrate scope (including N-acetyl and N-Ts substrates) and substituted indoles were obtained in good to excellent yields. The most distinctive feature of this method lies in the high selectivity for N-benzoylindole over benzoxazine, and this is the first example of Pd(II)-catalyzed synthesis of substituted N-benzoylindole. Notably, this new method was applied for the synthesis of key intermediate of indomethacin.
- Chang, Zhe,Dong, Zheng,Ma, Tong,Zhang, Yu,Zhao, Depeng,Zhao, Heng
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supporting information
(2020/03/19)
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- Intramolecular Aminoazidation of Unactivated Terminal Alkenes by Palladium-Catalyzed Reactions with Hydrogen Peroxide as the Oxidant
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The palladium-catalyzed aminoazidation of aminoalkenes yielding azidomethyl-substituted nitrogen-containing heterocycles was developed. The procedure requires oxidative conditions and occurs at room temperature in the presence of hydrogen peroxide and NaN3 as the azide source. These conditions provide selective exo-cyclization/azidation of the carbon-carbon double bond, furnishing a versatile approach toward five-, six-, and seven-membered heterocyclic rings.
- Beccalli, Egle M.,Broggini, Gianluigi,Foschi, Francesca,Lo Presti, Leonardo,Loro, Camilla,Oble, Julie,Poli, Giovanni,Sala, Roberto
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supporting information
(2020/02/28)
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- Generalized Chemoselective Transfer Hydrogenation/Hydrodeuteration
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A generalized, simple and efficient transfer hydrogenation of unsaturated bonds has been developed using HBPin and various proton reagents as hydrogen sources. The substrates, including alkenes, alkynes, aromatic heterocycles, aldehydes, ketones, imines, azo, nitro, epoxy and nitrile compounds, are all applied to this catalytic system. Various groups, which cannot survive under the Pd/C/H2 combination, are tolerated. The activity of the reactants was studied and the trends are as follows: styrene'diphenylmethanimine'benzaldehyde'azobenzene'nitrobenzene'quinoline'acetophenone'benzonitrile. Substrates bearing two or more different unsaturated bonds were also investigated and transfer hydrogenation occurred with excellent chemoselectivity. Nano-palladium catalyst in situ generated from Pd(OAc)2 and HBPin extremely improved the TH efficiency. Furthermore, chemoselective anti-Markovnikov hydrodeuteration of terminal aromatic olefins was achieved using D2O and HBPin via in situ HD generation and discrimination. (Figure presented.).
- Wang, Yong,Cao, Xinyi,Zhao, Leyao,Pi, Chao,Ji, Jingfei,Cui, Xiuling,Wu, Yangjie
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supporting information
p. 4119 - 4129
(2020/08/10)
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- On the Virtue of Indium in Reduction Reactions. A Comparison of Reductions Mediated by Indium and Zinc: Is Indium Metal an Effective Catalyst for Zinc Induced Reductions?
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Indium(0)-mediated reductions have been reported for the transformation of several functional groups (imines, oximes, nitro groups, isoxazolidines, and conjugated alkenes, among others), prompted by the opportunity of performing the reactions in aqueous media and green conditions. We describe here the comparison of several reactions using indium or the less expensive zinc, carried out in order to evaluate the effective advantages brought about indium metal. We found some reactions for which use of In is mandatory and others where Zn worked equally well or even better. The reduction of hydroxylamines to the corresponding amines was the only reduction for which use of In provided much better results than Zn and was also possible to apply an efficient catalytic version with use of 2–5 mol-% In in the presence of stoichiometric Zn. Applicability of this catalytic reduction to “one-pot” model processes is also demonstrated.
- Matassini, Camilla,Bonanni, Marco,Marradi, Marco,Cicchi, Stefano,Goti, Andrea
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supporting information
p. 1106 - 1113
(2019/12/24)
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- Scalable preparation of stable and reusable silica supported palladium nanoparticles as catalysts for N-alkylation of amines with alcohols
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The development of nanoparticles-based heterogeneous catalysts continues to be of scientific and industrial interest for the advancement of sustainable chemical processes. Notably, up-scaling the production of catalysts to sustain unique structural features, activities and selectivities is highly important and remains challenging. Herein, we report the expedient synthesis of Pd-nanoparticles as amination catalysts by the reduction of simple palladium salt on commercial silica using molecular hydrogen. The resulting Pd-nanoparticles constitute stable and reusable catalysts for the synthesis of various N-alkyl amines using borrowing hydrogen technology without the use of any base or additive. By applying this Pd-based catalyst, functionalized and structurally diverse N-alkylated amines as well as some selected drug molecules were synthesized in good to excellent yields. Practical and synthetic utility of this Pd-based amination protocol has been demonstrated by upscaling catalyst preparation and amination reactions to several grams-scales as well as recycling of catalyst. Noteworthy, this Pd-catalyst preparation has been up-scaled to kilogram scale and catalysts prepared in both small (1 g) and large-scale (kg) exhibited similar structural features and activity.
- Alshammari, Ahmad S.,Natte, Kishore,Kalevaru, Narayana V.,Bagabas, Abdulaziz,Jagadeesh, Rajenahally V.
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p. 141 - 149
(2020/01/06)
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- Exploiting the radical reactivity of diazaphosphinanes in hydrodehalogenations and cascade cyclizations
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The remarkable reducibility of diazaphosphinanes has been extensively applied in various hydrogenations, based on and yet limited by their well-known hydridic reactivity. Here we exploited their unprecedented radical reactivity to implement hydrodehalogenations and cascade cyclizations originally inaccessible by hydride transfer. These reactions feature a broad substrate scope, high efficiency and simplicity of manipulation. Mechanistic studies suggested a radical chain process in which a phosphinyl radical is generated in a catalytic cycle via hydrogen-atom transfer from diazaphosphinanes. The radical reactivity of diazaphosphinanes disclosed here differs from their well-established hydridic reactivity, and hence, opens a new avenue for diazaphosphinane applications in organic syntheses.
- Cheng, Jin-Pei,Yang, Jin-Dong,Zhang, Jingjing
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p. 4786 - 4790
(2020/06/18)
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- Discovery and characterization of an acridine radical photoreductant
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Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction1–4. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper5,6. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts7–11. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of ?3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported12. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. We demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.
- MacKenzie, Ian A.,Wang, Leifeng,Onuska, Nicholas P. R.,Williams, Olivia F.,Begam, Khadiza,Moran, Andrew M.,Dunietz, Barry D.,Nicewicz, David A.
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- Indole compound and synthesizing and application methods thereof
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The invention relates to an indole compound and synthesizing and application methods thereof. The indole compound is prepared by selecting specific substituent groups. Experiments find that the indolecompound can achieve good inhibiting effects on prostatic cancer, good in drug-resistance-proofness and low in side effects when applied as an anti-cancer drug; besides, the synthesizing method of the indole compound comprises subjecting a compound with the structure shown as the formula (II), palladium acetate, benzoquinones and organic acids to reaction in solvent to obtain the indole compoundwith the structure shown as the formula (I). Experiment results show that the synthesizing method of the indole compound is low in requirements on substrate and high in product yield.
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Paragraph 0076-0079
(2019/10/22)
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- Synthesis of Benzofuran and Indole Derivatives Catalyzed by Palladium on Carbon
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Benzofurans and indoles are key moieties in many natural products and pharmaceuticals. Herein, we describe a cheap and easy-to-execute strategy for the synthesis of benzofurans and indoles, employing Pd/C as the promoter. A variety of substituted allyl-anilines and allyl-phenols were converted into the desired products in good to excellent yields. Recycling of Pd/C was possible up to five cycles, keeping similar levels of reactivity.
- Savvidou, Anatoli,IoannisTzaras, Dimitrios,Koutoulogenis, Giorgos S.,Theodorou, Alexis,Kokotos, Christoforos G.
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supporting information
p. 3890 - 3897
(2019/06/27)
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- Dehydrative Allylation of Amine with Allyl Alcohol by Titanium Oxide Supported Molybdenum Oxide Catalyst
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The dehydrative allylation from allyl alcohol with amines to generate various allyl amines by MoO 3 /TiO 2 solid catalyst is described. The catalyst can be reused at least three times without a decrease of activity.
- Kon, Yoshihiro,Nakashima, Takuya,Fujitani, Tadahiro,Murayama, Toru,Ueda, Wataru
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supporting information
p. 287 - 292
(2019/02/12)
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- Catalyst-Free Reductive Coupling of Aromatic and Aliphatic Nitro Compounds with Organohalides
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A rare reductive coupling of nitro compounds with organohalides has been realized. The reaction is initiated by a partial reduction of the nitro group to a nitrenoid intermediate. Therefore, not only aromatic but also aliphatic nitro compounds are efficiently transformed into monoalkylated amines, with organohalides as the alkylating agent. Given the innate reactivity of the nitrenoid, a catalyst is not required, resulting in a high tolerance for aryl halide substituents in both starting materials.
- Rauser, Marian,Eckert, Raphael,Gerbershagen, Max,Niggemann, Meike
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supporting information
p. 6713 - 6717
(2019/04/14)
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- Charge-Storage Aromatic Amino Compounds for Nonvolatile Organic Transistor Memory Devices
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Here, charge-storage nonvolatile organic field-effect transistor (OFET) memory devices based on interfacial self-assembled molecules are proposed. The functional molecules contain various aromatic amino moieties (N-phenyl-N-pyridyl amino- (PyPN), N-phenyl amino- (PN), and N,N-diphenyl amino- (DPN)) which are linked by a propyl chain to a triethoxysilyl anchor group and act as the interface modifiers and the charge-storage elements. The PyPN-containing pentacene-based memory device (denoted as PyPN device) presents the memory window of 48.43 V, while PN and DPN devices show the memory windows of 24.88 and 8.34 V, respectively. The memory characteristic of the PyPN device can remain stable along with 150 continuous write-read-erase-read cycles. The morphology analysis confirms that three interfacial layers show aggregation due to the N atomic self-catalysis and hydrogen bonding effects. The large aggregate-covered PyPN layer has the full contact area with the pentacene molecules, leading to the high memory performance. In addition, the energy level matching between PyPN molecules and pentacene creates the smallest tunneling barrier and facilitates the injection of the hole carriers from pentacene to the PyPN layer. The experimental memory characteristics are well in agreement with the computational calculation.
- Zheng, Chaoyue,Tong, Tong,Hu, Yueming,Gu, Yuming,Wu, Huarui,Wu, Dequn,Meng, Hong,Yi, Mingdong,Ma, Jing,Gao, Deqing,Huang, Wei
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- Development and application of aromatic amines material with charge storage ability
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The invention mainly relates to designing and integrating an aromatic amines material with charge storage ability. The chemical structure is (img file='DSA0000160682420000011. TIF' wi='436' he='149'/). Ar1 in the structure is one in the following aromatic units: (img file='DSA0000160682420000012. TIF' wi='700' he='307'/); Ar2 in the structure is one in the following aromatic units: (img file='DSA0000160682420000013. TIF' wi='700' he='305'/). In the structure, n is 1-16 alkyl straight chain, X=CI, OCH3 or OC2H5. The aromatic amines material with the charge storage ability can form a charge storage layer on the surface of a dielectric layer SiO2 and the charge storage layer can be applied to non-volatile organic field effect transistor memory, which displays wide application prospect in thefields of organic memory, organic photodetector, organic light emitting and the like.
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Paragraph 0035; 0037-0039
(2018/10/19)
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- Photocatalytic Synthesis of γ-Lactones from Alkenes: High-Resolution Mass Spectrometry as a Tool to Study Photoredox Reactions
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A mild photocatalytic manifold for the synthesis of γ-lactones has been developed. Utilizing Ru(bpy)3Cl2 as the photocatalyst, a cheap and reproducible synthetic protocol for γ-lactones has been introduced. Mechanistic studies revealed the successful monitoring of photocatalytic reactions and radical intermediates via high-resolution mass spectrometry.
- Triandafillidi, Ierasia,Kokotou, Maroula G.,Kokotos, Christoforos G.
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supporting information
p. 36 - 39
(2018/01/17)
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- Aerobic intramolecular aminothiocyanation of unactivated alkenes promoted by in situ generated iodine thiocyanate
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Aerobic intramolecular aminothiocyanation of unactivated alkenes has been developed by in situ generated iodine thiocyanate under open-flask conditions. This protocol provides a concise and efficient method for synthesizing SCN-containing pyrrolidine, piperidine and indoline derivatives with isolated yields of up to 87%. Furthermore, mixing iodine and sodium thiocyanate with oxygen afforded iodine thiocyanate (ISCN) and dithiocyanatoiodate [I(SCN)2]- which were testified by liquid chromatography mass spectrometry. A mechanistic investigation indicates that iodonium ion and sulfonium ion intermediates might be involved in this transformation.
- Feng, Yangyang,Hussain, Muhammad Ijaz,Zhang, Xiaohui,Shi, Jian,Hu, Wen,Xiong, Yan
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supporting information
p. 2669 - 2676
(2018/05/04)
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- One-pot Construction of Difluorinated Pyrrolizidine and Indolizidine Scaffolds via Copper-Catalyzed Radical Cascade Annulation
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A convenient approach to the synthesis of diverse difluorinated nitrogen-containing polycycles via a copper-catalyzed radical cascade annulation of amine-containing olefins and ethyl bromodifluoroacetate was developed. Three new bonds, including a Csp3 ?CF2 and two C?N bonds, are forged simultaneously in this strategy. Through this strategy, a series of difluorinated pyrrolizidine and indolizidine derivatives have been conveniently synthesized in good yields. (Figure presented.).
- Wang, Xiaoyang,Li, Miao,Yang, Yanyan,Guo, Minjie,Tang, Xiangyang,Wang, Guangwei
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supporting information
p. 2151 - 2156
(2018/04/26)
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- Copper immobilized at a covalent organic framework: An efficient and recyclable heterogeneous catalyst for the Chan-Lam coupling reaction of aryl boronic acids and amines
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A polyimide covalent organic framework (PI-COF) with high thermal and chemical stabilities has been readily prepared from commercially available and inexpensive reagents and was employed as an effective support for heterogeneous copper. It was demonstrated that the obtained Cu@PI-COF is a highly active heterogeneous catalyst which can effectively promote the Chan-Lam coupling reaction of aryl boronic acids and amines in an open flask without the aid of any base or additive. In addition, the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least eight cycles without any observable change in structure and catalytic activity.
- Han, Yi,Zhang, Mo,Zhang, Ya-Qing,Zhang, Zhan-Hui
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p. 4891 - 4900
(2018/11/21)
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- A Simple, Broad-Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols
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The preparation of allylic amines is traditionally accomplished by reactions of amines with reactive electrophiles, such as allylic halides, sulfonates, or oxyphosphonium species; such methods involve hazardous reagents, generate stoichiometric waste streams, and often suffer from side reactions (such as overalkylation). We report here the first broad-scope nickel-catalysed direct amination of allyl alcohols: An inexpensive NiII/Zn couple enables the allylation of primary, secondary, and electron-deficient amines without the need for glove-box techniques. Under mild conditions, primary and secondary aliphatic amines react smoothly with a range of allyl alcohols, giving secondary and tertiary amines efficiently. This “totally catalytic” method can also be applied to electron-deficient nitrogen nucleophiles; the practicality of the process was demonstrated in an efficient, gram-scale preparation of the calcium antagonist drug substance flunarizine (Sibelium).
- Sweeney, Joseph B.,Ball, Anthony K.,Lawrence, Philippa A.,Sinclair, Mackenzie C.,Smith, Luke J.
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supporting information
p. 10202 - 10206
(2018/08/06)
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- Intramolecular alkene hydroamination and degradation of amidines: Divergent behavior of rare earth metal amidinate intermediates
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Direct N-H addition of amidines to alkenes is a highly valuable but challenging transformation that remains elusive. Now, the intramolecular hydroamidination of N-alkenylamidines is achieved by using a rare earth catalyst, which provides an efficient and atom-economical approach for substituted imidazolines and tetrahydropyrimidines. Moreover, a mild and efficient method for the catalytic degradation of amidines to give amines and nitriles is also developed. Additionally, amidine reconstruction followed by an intramolecular alkene hydroamidination strategy for the synthesis of substituted imidazolines and tetrahydropyrimidines from secondary enamines and inactive amidines has also been established, which may circumvent the need for some unavailable starting materials. The mechanistic studies prove that these reactions proceed via a key lanthanide amidinate intermediate that can undergo substrate- and amine-controlled chemodivergent transformations: intramolecular alkene insertion, nitrile extrusion, amidinate reconstruction, or a combination of the reactions. The results presented here not only demonstrate the synthetic potential and versatility of alkene hydroamidination with substrates, but also provide a good insight into the factors that promote or deter the hydroamidination of alkenes.
- Zhang, Dexing,Liu, Ruiting,Zhou, Xigeng
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p. 5573 - 5581
(2018/11/20)
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- Method for generating nitrile and amine by means of rare-earth catalytic amidines compound degradation
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The invention belongs to the technical field of chemical engineering, and particularly discloses a method for generating nitrile and amine by means of rare-earth catalytic amidines compound degradation. The method includes directly degrading amidines compounds in rare-earth catalytic systems to generate the corresponding nitrile and the corresponding amine. The method has the advantages that the method is wide in application range and easy and convenient to operate; the nitrile can be generated by the aid of the method under mild conditions in a high-yield manner, and the method is high in reaction selectivity.
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Paragraph 0012
(2018/10/19)
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- Palladium-Catalyzed Fluoroalkylative Cyclization of Olefins
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A palladium-catalyzed fluoroalkylative cyclization of olefins with readily available Rf-I reagents to afford the corresponding fluoroalkylated 2,3-dihydrobenzofuran and indolin derivatives with moderate to excellent yields is reported. This novel procedure provides an efficient method for the construction of Csp3-CF2 and C-O/N bonds in one step. A wide range of functional groups are tolerated. It is proposed that a radical/SET (single electron transfer) pathway proceeding via the fluoroalkyl radical may be involved in the catalytic cycle.
- Liao, Jianhua,Fan, Lianfeng,Guo, Wei,Zhang, Zhenming,Li, Jiawei,Zhu, Chuanle,Ren, Yanwei,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 1008 - 1011
(2017/03/15)
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- Green Organocatalytic Synthesis of Indolines and Pyrrolidines from Alkenes
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Employing a green and efficient 2,2,2-trifluoroacetophenone-catalyzed oxidation of alkenes, which utilizes H2O2 as the green oxidant, a novel and sustainable synthesis of indolines and pyrrolidines was developed. This constitutes a cheap, general and environmentally-friendly protocol for the synthesis of substituted nitrogen-containing heterocycles. A variety of substitution patterns, both aromatic and aliphatic moieties, are well tolerated leading to the desired nitrogen heterocycles in good to excellent yields. (Figure presented.).
- Theodorou, Alexis,Kokotos, Christoforos G.
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supporting information
p. 1577 - 1581
(2017/05/05)
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- Copper-Promoted Intramolecular Aminotrifluoromethylation of Alkenes with Langlois Reagent as the Trifluoromethyl Source
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A novel approach for copper-promoted intramolecular aminotrifluoromethylation of alkenes using inexpensive CF3SO2Na as the trifluoromethyl source is described. The feature of this method is the concurrent construction of a five-membered ring and a C-CF3 bond in the simple copper salt/TBHP system. A gram-scale reaction was tested with a slight decrease in the yield. This protocol provides an operationally simple, step-economical and synthetically useful access to a variety of trifluoromethyl indolines, pyrrolidines and lactams.
- Zhang, Hong-Yu,Huo, Wenge,Ge, Chao,Zhao, Jiquan,Zhang, Yuecheng
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supporting information
p. 962 - 965
(2017/05/05)
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- Platinum(II)-Crosslinked Single-Chain Nanoparticles: An Approach towards Recyclable Homogeneous Catalysts
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We introduce the synthesis and in-depth characterization of platinum(II)-crosslinked single-chain nanoparticles (PtII-SCNPs) to demonstrate their application as a recyclable homogeneous catalyst. Specifically, a linear precursor copolymer of styrene and 4-(diphenylphosphino)styrene was synthesized via nitroxide-mediated polymerization. The triarylphosphine ligand moieties along the backbone allowed for the intramolecular crosslinking of single chains via the addition of [Pt(1,5-cyclooctadiene)Cl2] in dilute solution. The successful formation of well-defined PtII-SCNPs was evidenced by size exclusion chromatography, dynamic light scattering, nuclear magnetic resonance (1H, 31P{1H}, 195Pt), and diffusion-ordered spectroscopy. Finally, the activity of the PtII-SCNPs as homogeneous, yet recyclable catalyst was successfully demonstrated using the example of the amination of allyl alcohol.
- Kn?fel, Nicolai D.,Rothfuss, Hannah,Willenbacher, Johannes,Barner-Kowollik, Christopher,Roesky, Peter W.
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supporting information
p. 4950 - 4954
(2017/04/24)
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- MANUFACTURING METHOD OF ALKENYLAMINE
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SOLUTION: A manufacturing method of alkenylamine for manufacturing alkenylamine by reacting alkenyl halide and amine, includes conducting the above described reaction in presence of a solution containing alkali metal hydroxide of excess quantity for neutralizing hydrogen halide which is a by-product in the above described reaction, and then separating an oil phase containing generated alkenylamine and a water phase, where unreacted alkali metal hydroxide and alkali metal halide generated by neutralizing hydrogen halide which is a by-product in the above described reaction with alkali metal hydroxide are dissolved, and purifying the resulting oil phase to obtain alkenylamine. EFFECT: Alkenylamine can be manufactured at high yield even with a small used amount of amine to alkenyl halide. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT
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Paragraph 0034
(2017/06/19)
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- Electrophilic Amination with Nitroarenes
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An exceptionally general electrophilic amination, which directly transforms commercially available nitroarenes into alkylated aromatic aminoboranes with zinc organyl compounds was developed. The reaction starts with a two-step partial reduction of the nitro group to a nitrenoid, which is used in situ as the electrophilic amination reagent. To facilitate isolation, the resulting air- and moisture-sensitive aminoboranes were reacted with a range of electrophiles. The method not only represents a direct transformation of nitro compounds into electrophilic amination reagents but also provides an elegant alternative to dehydrocoupling methods for the generation of aminoboranes.
- Rauser, Marian,Ascheberg, Christoph,Niggemann, Meike
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supporting information
p. 11570 - 11574
(2017/09/11)
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- Thioamination of Alkenes with Hypervalent Iodine Reagents
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An efficient thioamination of alkenes mediated by iodine(III) reagents is described. The use of different sulfur nucleophiles allows the flexible synthesis of 1,2-aminothiols from alkenes. By employing chiral iodine(III) reagents, a stereoselective version of the thioamination protocol has also been developed.
- Mizar, Pushpak,Niebuhr, Rebecca,Hutchings, Matthew,Farooq, Umar,Wirth, Thomas
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supporting information
p. 1614 - 1617
(2016/02/20)
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- Palladium-Catalyzed Aerobic Intramolecular Aminoacetoxylation of Alkenes Enabled by Catalytic Nitrate
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A mild aerobic intramolecular aminoacetoxylation method for the synthesis of pyrrolidine and indoline derivatives was achieved using molecular oxygen as the oxidant. A catalytic NOx species acts as an electron transfer mediator to access a high-valent palladium intermediate as the presumed active oxidant.
- Li, Jiaming,Grubbs, Robert H.,Stoltz, Brian M.
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supporting information
p. 5449 - 5451
(2016/11/17)
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- Iron-Based Imidazolium Salts as Versatile Catalysts for the Synthesis of Quinolines and 2- and 4-Allylanilines by Allylic Substitution of Alcohols
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Readily available iron(III)-based imidazolium salts have proven to be very versatile catalysts for the allylic substitution reaction of alcohols with anilines, allowing the synthesis of quinolines, 2-allylanilines and 4-allylanilines just by modulating the reaction conditions. Noteworthy, the formation of quinoline derivatives proceeds by ortho-allylation of the corresponding aniline and subsequent oxidative cyclization mediated by atmospheric oxygen. The reaction using anilines as nucleophiles is selective to the C-alkylation versus the N-alkylation, under any reaction conditions studied. (Figure presented.).
- Trillo, Paz,Pastor, Isidro M.
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p. 2929 - 2939
(2016/09/16)
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- Nickel(0)-Catalyzed N-Allylation of Amides and p-Toluenesulfonamide with Allylic Alcohols under Neat and Neutral Conditions
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Nickel(0)-catalyzed direct N-allylation of amides and p-toluenesulfonamide with allylic alcohols took place in the presence of Ni0–diphosphine complexes. The corresponding N-allylated (and/or N,N-diallylated) products were obtained in moderate to high yields under neutral conditions.
- Azizi, Mohamed Salah,Edder, Youssef,Karim, Abdallah,Sauthier, Mathieu
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p. 3796 - 3803
(2016/08/16)
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- Facet-Dependent Catalytic Activity of Palladium Nanocrystals in Tsuji-Trost Allylic Amination Reactions with Product Selectivity
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Pd nanocubes, cuboctahedra, and octahedra with good size control were used to catalyze C-N bond formation in the Tsuji-Trost allylic amination reaction of aniline. Nanocubes gave either monoallylaniline or diallylaniline depending on the amount of allyl bromide used, but the octahedra and cuboctahedra only gave mixtures of monoallylaniline and diallylaniline under the same reaction conditions. The Pd nanocubes were stable over multiple cycles of the reaction. The cubes and octahedra were demonstrated to catalyze the amination reaction by using a wide variety of substituted anilines, but the cubes were the best catalyst with consistently the highest efficiency, product yield, and product selectivity. This work demonstrates that the use of metal nanocrystals with proper facet control is important for catalyzing coupling reactions with product selectivity. Getting into shapes: Pd nanocubes, cuboctahedra, and octahedra with good size control are used to catalyze C-N bond formation in the Tsuji-Trost allylic amination reaction of aniline. The Pd nanocube catalyst gives good product selectivity, whereas the Pd octahedra and cuboctahedra catalysts yield mixtures of products under the same reaction conditions. Furthermore, Pd nanocubes are stable over multiple reaction cycles.
- Chanda, Kaushik,Rej, Sourav,Liu, Shu-Ya,Huang, Michael H.
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p. 1813 - 1817
(2015/06/23)
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- Copper(II)-catalyzed enantioselective intramolecular cyclization of N-alkenylureas
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The first Cu(II)-catalyzed highly enantioselective intramolecular cyclization of N-alkenylureas was developed for the concise assembly of chiral vicinal diamino bicyclic heterocycles. Facile removal of carbonyl group of the carbamido moiety allowed for ready access to enantioenriched cyclic vicinal diamines.
- Fu, Shaomin,Yang, Honghao,Deng, Yuanfu,Jiang, Huanfeng,Zeng, Wei,Li, Guoqiang
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supporting information
p. 1018 - 1021
(2015/03/30)
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- Copper-Promoted Tandem Reaction of Azobenzenes with Allyl Bromides via N=N Bond Cleavage for the Regioselective Synthesis of Quinolines
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A copper-promoted tandem reaction of a variety of azobenzenes and allyl bromides via N=N bond cleavage to regioselectively construct quinoline derivatives has been developed. The azobenzenes act as not only construction units but also an oxidant for quinoline formation.
- Yi, Xiangli,Xi, Chanjuan
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supporting information
p. 5836 - 5839
(2015/12/11)
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- Palladium-catalyzed direct coupling of 2-vinylanilines and isocyanides: An efficient synthesis of 2-aminoquinolines
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Palladium-catalyzed oxidative coupling of 2-vinylanilines and isocyanides constitutes a direct, facile, and efficient approach to 2-aminoquinolines. The procedure, employing palladium acetate and silver carbonate, is attractive in terms of assembly efficiency, functional group tolerance, and operational simplicity. A variety of 2-aminoquinolines were prepared in good to excellent yields.
- Wang, Lijie,Ferguson, Jamie,Zeng, Fanlong
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supporting information
p. 11486 - 11491
(2015/12/04)
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- Copper-catalyzed radical cascade cyclization for the synthesis of phosphorated indolines
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A novel and convenient approach to the synthesis of various phosphorated indolines via a copper-catalyzed radical cascade cyclization reaction has been developed. The reaction employs cheap copper as the catalyst and K2S2O8 as the oxidant under mild conditions. Various alkenes and P-radical precursors are compatible with this transformation. Preliminary mechanistic studies reveal that the addition of the P-radical may initiate the reaction, and then oxidative cyclization may be achieved to afford the desired product. This journal is
- Zhang, Hong-Yu,Mao, Liu-Liang,Yang, Bin,Yang, Shang-Dong
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supporting information
p. 4101 - 4104
(2015/03/30)
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- Pentacoordinated Carboxylate π-Allyl Nickel Complexes as Key Intermediates for the Ni-Catalyzed Direct Amination of Allylic Alcohols
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Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5-cyclooctadiene)2] and 1,1′-bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu4NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu4NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η3-allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.
- Kita, Yusuke,Sakaguchi, Hironobu,Hoshimoto, Yoichi,Nakauchi, Daisuke,Nakahara, Yasuhito,Carpentier, Jean-Fran?ois,Ogoshi, Sensuke,Mashima, Kazushi
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supporting information
p. 14571 - 14578
(2015/10/05)
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- Cycloamidination of Aminoalkenes with Nitriles: Synthesis of Substituted 2-Imidazolines and Tetrahydropyrimidines
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The first catalytic cycloamidination of aminoalkenes with nitriles has been achieved by using rare-earth complexes. This reaction is equivalent to the desired intramolecular hydroamination of alkenylamidines, and allows a new direct access to substituted 2-imidazolines and tetrahydropyrimidines in high yields under operationally simple reaction conditions. Moreover, the methodology is also efficient for synthesis of symmetric and unsymmetric bridged diimidazolines. Compared with the traditional stepwise-mediated synthetic approaches, the present method avoids the use of additives and harsh reaction conditions, and thus leads to a completely different product distribution. Mechanistic data suggest that the reaction involves the initial NH activation by lanthanide complex followed by nitrile insertion into a Ln-N bond to form an amidinate lanthanide intermediate which undergoes the cyclization.
- Huang, Shujian,Shao, Yinlin,Zhang, Lixin,Zhou, Xigeng
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supporting information
p. 14452 - 14456
(2016/01/25)
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- Highly selective N-allylation of anilines under microwave irradiation
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An easy and rapid procedure for the preparation of a variety of mono- and bis-allylated anilines via the reaction of allyl bromide with a wide range of anilines under microwave irradiation is described. This approach allows use of mild conditions and short reaction times to give high selectivities and excellent yields.
- Liu, Meiyu,Wang, Xie,Sun, Xiaoliang,He, Wei
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p. 2711 - 2714
(2014/05/06)
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- Synthesis of novel [3,1]-benzothiazepine and [3,1]-benzoxazepine derivatives with antitumoral activity
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A new method for the synthesis of [3,1]-benzothiazepines and [3,1]-benzoxazepines from the reaction of C-allylanilines and isothiocyanates or isocyanates without the need for the isolation of any intermediate is described. The compounds were obtained in good to moderate yields and some exhibited cytotoxic activity against tumor cell lines. This journal is the Partner Organisations 2014.
- Martinez, Walter R.,Militao, Gardenia C. G.,Da Silva, Teresinha G.,Silva, Ricardo O.,Menezes, Paulo H.
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p. 14715 - 14718
(2014/04/17)
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- Palladium-catalyzed selective aminoamidation and aminocyanation of alkenes using isonitrile as amide and cyanide sources
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A mild and efficient palladium-catalyzed intermolecular aminoamidation and aminocyanation reaction of alkenes with a broad substrate scope has been developed. This cyclization process provides a valuable synthetic tool for obtaining substituted indolines, tetrahydroisoquinolines and pyrrolidines in good to excellent yields. This journal is
- Jiang, Huanfeng,Gao, Hanling,Liu, Bifu,Wu, Wanqing
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supporting information
p. 15348 - 15351
(2015/01/08)
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- Organocatalytic Stereoselective Iodoamination of Alkenes
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A new chiral thiohydantoin catalyst is used for the stereoselective iodoamination of alkenes. N-iodosuccinimide as the source of the electrophilic iodine is activated by catalytic amounts of different additives which also influence the regioselectivity of some cyclizations.
- Mizar, Pushpak,Burrelli, Alessandra,Günther, Erika,S?ftje, Martin,Farooq, Umar,Wirth, Thomas
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supporting information
p. 13113 - 13116
(2016/02/19)
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- N-arylation of amines: C-N coupling of amines with arylboronic acids using Fe3O4 magnetic nanoparticles-supported EDTA-Cu(ii) complex in water
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Fe3O4 magnetic nanoparticles-supported EDTA-copper(ii) complex (Fe3O4-EDTA-Cu(ii)) has been prepared and characterized by TEM, SEM, XRD, VSM, TGA, and FT-IR spectrometers. The catalyst was applied for the C-N coupling of arylboronic acids with amines for the preparation of N-aryl compounds. Recovery tests confirm that the catalyst can be easily recovered and reused up to eight times without significant loss of its catalytic activity.
- Mostafalu, Ramin,Kaboudin, Babak,Kazemi, Foad,Yokomatsu, Tsutomu
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p. 49273 - 49279
(2014/12/10)
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- Metal-free reductive cleavage of C-N and S-N bonds by photoactivated electron transfer from a neutral organic donor
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A photoactivated neutral organic super electron donor cleaves challenging arenesulfonamides derived from dialkylamines at room temperature. It also cleaves a)ArC-NR and b)ArN-C bonds. This study also highlights the assistance given to these cleavage reactions by the groups attached to N in (a) and to C in (b), by lowering LUMO energies and by stabilizing the products of fragmentation. Radical fragmentations: Electron transfer from the photoactivated neutral electron donor 1 delivers high yields of S-N and C-N cleavage products for a range of nitrogen-containing species. These reactions proceed at room temperature and under mild reaction conditions in the absence of any metal reagents. DMF=N,N-dimethylformamide, Ts=4-toluenesulfonyl.
- O'Sullivan, Steven,Doni, Eswararao,Tuttle, Tell,Murphy, John A.
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supporting information
p. 474 - 478
(2014/01/23)
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