- Nano PdAu Bimetallic Alloy as an Effective Catalyst for the Buchwald-Hartwig Reaction
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It is highly challenging but desirable to develop efficient heterogeneous catalysts for C-Cl bond activation in coupling reactions. Here, we succeeded in synthesizing bimetallic Pd-Au nanoparticles through a convenient one-pot wet chemical route. The composition and alloyed structure of the as-prepared nanoparticles were fully characterized. We have evaluated the catalytic activity of these Pd-Au alloy catalysts in Buchwald-Hartwig reactions of aryl chlorides. The excellent catalytic activity of the as-obtained Pd-Au nanoparticles indicates that exploiting the catalytic power of nano-alloy catalysts could enable effective C-Cl bond activation suitable for cross-coupling reactions.
- Chen, Zheng,Wang, Shuo,Lian, Chao,Liu, Yuxi,Wang, Dingsheng,Chen, Chen,Peng, Qing,Li, Yadong
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- A practical removal method of camphorsultam
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A mild and efficient removal of camphorsultam was realized using tetrabutylammonium hydrogen peroxide as a key reagent.
- Hasegawa, Tomoyuki,Yamamoto, Hisashi
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- A base-free Chan–Lam reaction catalyzed by an easily assembled Cu(II)-carboxylate metal-organic framework
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A new copper(II) metal-organic framework is constructed as a sustainable copper heterogeneous catalyst. Cu-DPTCA, with high catalytic activity, can effectively promote the Chan–Lam coupling reaction of arylboronic acids and amines without adding any base or additive.
- Ma, Ruixuan,Qin, Jianhua,Shi, Lei,Zhang, Xinhai
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- PHOTOCHEMISTRY OF 1,3-DIPHENYLTRIAZENE IN VARIOUS MEDIA. II: SOLID STATE PHOTOLYSIS.
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Solid 1,3-diphenyltriazene (DPT) has been photolyzed at 290 nm and 360 nm. The distribution of the photoproducts showed that recombination of the radicals produced after photochemical excitation was governed by a 'cage effect' favoring a minimum of motion of the recombining radicals. In many details the results differ from observations on the photochemistry of DPT in liquid solutions. The photolysis of DPT in polymethylmethacrylate films, however, resembles the photochemistry of DPT in liquid solutions.
- Baro,Dudek,Luther,Troe
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- One-Step Pyrolysis Preparation of 1.1.1 Oriented Gold Nanoplatelets Supported on Graphene and Six Orders of Magnitude Enhancement of the Resulting Catalytic Activity
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Pyrolysis of chitosan films containing Au3+ renders 1.1.1 oriented Au nanoplatelets (20 nm lateral size, 3-4 nm height) on a few layers of N-doped graphene (${overline {{rm{Au}}} }$/fl-G), while the lateral sides were 0.0.1 oriented. Comparison of the catalytic activity of ${overline {{rm{Au}}} }$/fl-G films with powders of unoriented Au NPs supported on graphene showed that ${overline {{rm{Au}}} }$/fl-G films exhibit six orders of magnitude enhancement for three gold-catalyzed reactions, namely, Ullmann-like homocoupling, C-N cross coupling, and the oxidative coupling of benzene to benzoic acid. This enhancement is the result of the defined morphology, facet orientation of Au nanocrystals, and strong gold-graphene interaction.
- Primo, Ana,Esteve-Adell, Ivan,Coman, Simona N.,Candu, Natalia,Parvulescu, Vasile I.,Garcia, Hermenegildo
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- Palladium-Imidazolium N-Heterocyclic Carbene-Catalyzed Carbonylative Amidation with Boronic Acids, Aryl Diazonium Ions, and Ammonia
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Aryl diazonium tetrafluoroborates have been coupled with arylboron compounds, carbon monoxide, and ammonia to give aryl amides in high yields. A saturated N-heterocyclic carbene (NHC) ligand, H2IPr was used with palladium(II) acetate to give the active catalyst. A mechanism is proposed for this novel four-component coupling reaction.
- Ma, Yudao,Song, Chun,Chai, Qiang,Ma, Changqin,Andrus, Merritt B.
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- Replacing sulfonate by carboxylate: Application of pyridyliminocarboxylato copper(II) complexes in rac-lactide polymerization and Chan-Evans-Lam coupling
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Copper(II) complexes carrying pyridylmethyleneaminobenzoate or-propanoate ligands, LCuX, were prepared in one-pot reactions from pyridinecarboxaldehyde, aminobenzoic acid or β-alanine, and CuX2 (X = Cl, NO3, OAc, or OTf). All complexes were characterized by single-crystal X-ray diffraction studies and formed either dimers, tetramers, or coordination polymers. Attempted preparation of the respective alkoxide complexes, LCu(OR), was unsuccessful, but use of LCuX/NaOMe mixtures in rac-lactide polymerization indicated under some conditions coordination-insertion polymerization via a copper alkoxide as the mechanism. The complexes performed poorly in rac-lactide polymerization, showing low activities (12 h to completion at 140 °C), low to moderate heterotacticity (Pr = 0.6-0.8), and poor polymer molecular weight control (intramolecular transesterification). They were competent catalysts for Chan-Evans-Lam couplings with phenylboronic acid, without any indication of side reactions such as deboration or aryl homocoupling. The complexes were active in undried methanol, without addition of base, ligand, or molecular sieves. Aniline, n-octylamine, and cyclohexylamine were coupled quantitatively under identical reaction conditions. There is only little influence of the anion on activities (less than a factor of 2) but a strong influence on induction periods. The complexes were not active in CEL coupling with alcohols, phenols, or alkylboronic acids.
- Hardouin Duparc, Valérie,Dimeck, Clémentine,Schaper, Frank
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- Reactions of Diarylnitrenium Ions with Electron Rich Alkenes: An Experimental and Theoretical Study
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Photolysis of N-(diphenylamino)-2,4,6-trimethylpyridinium tetrafluoroborate (1a) and N-[bis(4-methylphenyl)amino]-2,4,6-trimethylpyridinium salt (1b) gives products attributable to diarylnitrenium ion (Ar2N+, 2). The major products of these reactions include products from nucleophilic addition of various π-nucleophiles (e.g. electron rich alkenes) to the ortho and para positions of one of the phenyl rings. Nanosecond and EPR spectroscopy show that radicals also form. These radicals are thought to give rise to the diarylamines isolated as minor products from the photolysis of la and 1b. In addition to the para addition products and Ph2NH, N-phenylindoles and N-phenylindolinones are isolated when silyl enol ethers and silyl ketene acetals are used as trapping agents, respectively. The indoles and indolinones are generated from initial addition of the nucleophile to the ortho position on 2 followed by cyclization of the resulting intermediate. A product resulting from N addition of the nucleophile to 2 is isolated only when silyl ketene acetals are used. A number of electronic sturcture calculations at different levels of molecular orbital and density functional theory were carried out on Ph2N+. There do not seem to be effects associated with either the charge distribution or the LUMO that would strongly influence ortho/para/N selectivity in nucleophilic trapping. Laser flash photolysis on la provides absolute rate constants for the nucleophilic addition of various alkenes to Ph2N+. These fall in the range of 109-1010 M-1 s-1 and correlate with the oxidation potential of the alkene. From these data it is clear that the more easily oxidized the alkene the faster it will react with Ph2N+.
- Moran, Ricardo J.,Cramer, Christopher,Falvey, Daniel E.
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- Theoretical and Experimental Studies: Cu(I)/Cu(II) Catalytic Cycle in CuI/Oxalamide-Promoted C-N Bond Formation
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In modern Ullmann-Goldberg reactions, cheaper aryl chlorides are poor substrates. Recently, attention has been paid to facile CuI/oxalamide-promoted arylation of heteroatoms (N, O, and S) using cheaper aryl chlorides. However, the mechanism of the reaction and the role of oxalamides have not yet been investigated. In the present investigation, theoretical (density functional theory) and supporting in situ 1H NMR spectroscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy, and cyclic voltammetry studies have been performed to provide insight into the various aspects of the mechanism. Five different possible pathways have been investigated. [LCu(NHNu)] is the active copper catalytic species, in which L (oxalamide) coordinates Cu(I) through both C=O groups. Our studies show that the reaction follows an outer-sphere single-electron transfer pathway. Moreover, these studies also address the reason for the deactivation of a copper catalyst.
- Morarji, Devita V.,Gurjar, Kamlesh K.
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- Copper(II) hydroxide complexes of N-heterocyclic carbenes and catalytic oxidative amination of arylboronic acids
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Reactions of the imidazolium salts or their corresponding silver carbene complexes with copper powder afforded unusual copper(II) hydroxide complexes of N-heterocyclic carbenes: [Cu2(μ-OH)(L1)](PF6) 2 (2; L1 = 3,5-bis(N-picolylimidazolylidenylmethy1)pyrazolate), [Cu4(μ3-OH)2(L2)2](PF 6)4 (3; L2 = 3,5-bis(N-pyridylimidazolylidenylmethy1) pyrazolate), and [Cu4(μ3-OH)2(L3) 2](PF6)4 (4; L3 = 3,5-bis(N- pyrimidylimidazolylidenylmethy1)pyrazolate). The same reaction of 3,5-bis(N-thiophenylimidazoliumylmethy1)pyrazole yielded a dinuclear Cu(II)-NHC complex, [Cu2(L4)2] (PF6)2 (5; L4 = 3,5-bis(N-thiophenylimidazolylidenylmethy1)pyrazolate). The complexes have been fully characterized by X-ray diffraction analysis, elemental analysis, and IR and ESI-MS spectra. A catalytic study shows that complex 4 is highly active in the N-arylation reactions of imidazoles and aromatic amines with arylboronic acids in methanol at room temperature under base-free conditions.
- Liu, Bo,Liu, Bin,Zhou, Yongbo,Chen, Wanzhi
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- Nickel(II) thiolates derived from transmetallation reaction of [Zn(Tab)4](PF6)2 with Ni(II) ions and their catalytic activity toward the CN coupling reactions
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Reactions of NiCl2·6H2O or Ni(ClO 4)2·6H2O with 2,2′-bipyridine (2,2′-bipy), or 2-bis(diphenylphosphino)ethane (dppe) or 1,4-bis(diphenylphosphino)butane (dppb) followed by addition of [Zn(Tab) 4](PF6)2 (1) resulted in the formation of one trinuclear cationic complex [(2,2′-bipy)4Ni3(μ- Tab)4]Cl0.5(PF6)5.5 (2), one mononuclear cationic complex [Ni(Tab)2(dppe)](PF6) 2 (3), and one dinuclear cationic complex [Ni2(dppb)(μ- Tab)2(Tab)2](PF6)2(ClO 4)2 (4). Complexes 2-4 were characterized by elemental analysis, IR, UV-vis, 1H and 31P NMR, and single-crystal X-ray diffraction. In the [(2,2′-bipy)4Ni3(μ-Tab) 4]6 + hexacation of 2, the central Ni(II) atom is connected to two [Ni(2,2′-bipy)2]2 + fragments by two pairs of μ-Tab ligands, forming a linear trinuclear cationic structure. The Ni(II) center of the dication of 3 is tetrahedrally coordinated by two S atoms from two Tab ligands and two P atoms of one dppe ligand. Complex 4 has a dimeric cationic structure in which two [(Tab)Ni]2 + species are linked by a pair of μ-Tab ligands and one dppb ligand. Complexes 2-4 displayed high catalytic activity toward the cross-coupling reactions of arylboronic acids and amines to produce N-arylated amines.
- Shi, Jing,Li, Fu-Ling,Li, Hong-Xi,Wang, Fan,Yu, Hong,Ren, Zhi-Gang,Zhang, Wen-Hua,Lang, Jian-Ping
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- Vapour-Phase Substitution of Chlorobenzene with Ammonia Catalyzed by Copper-Exchanged Zeolites
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The nucleophilic substitution of chlorobenzene with ammonia, leading to aniline, was investigated over various copper-exchanged catalysts using vapour-phase reactants.Benzene and diphenylamine were formed as side-products.The zeolites tested (Cu-L, Cu-modernite, Cu-Y, Cu-ZSM-5, and Cu-beta) gave better results than copper-containing silica-alumina, because of the high deactivation rate of the latter.On zeolites Cu-L, Cu-modernite, and Cu-ZSM-5, substitution prevailed: with Cu-modernite and Cu-ZSM-5, aniline selectivities of 90-94percent were obtained.In contrast, reduction towards benzene was pronounced on Cu-beta and especially on Cu-Y.In more detailed studies with Cu-modernite, two deactivation regimes were observed, related to the reaction temperature.With Cu-L, the dehalogenation towards benzene was investigated: it is ascribed to copper reduction, followed by the reduction of chlorobenzene with the copper(0) particles thus obtained.
- Burgers, M. H. W.,Bekkum, H. van
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- Novel Burgess reagent mediated C-to-N aryl migration reaction in nitrones
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Nitrones undergo useful transformations with Burgess reagent. The reaction ostensibly involves a [3 + 2] annulation across a σ-bond followed by rearrangement involving C-to-N aryl migration. On the basis of available experimental evidence, plausible mechanisms for the rearrangement and the overall conversion have been proposed.
- Sajitha,Prathapan,Unnikrishnan
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- Reduction of N-nitrosodiphenylamine to the corresponding hydrazine by guinea pig liver preparations
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The present study provides first evidence for enzymatic reduction of a noncyclic nitrosamine to the corresponding hydrazine. Under anaerobic conditions, N-nitrosodiphenylamine was reduced to 1,1-diphenylhydrazine by guinea pig liver 9,000 xg supernatant or cytosol in the presence of an NADPH-generating system and FAD, or NADH and FAD. However, guinea pig liver microsomes did not catalyze the reduction of the nitrosamine at all. The reduction product was isolated from the reaction mixture and identified unequivocally by comparing with authentic samples its mass and UV spectra, and its behavior in HPLC and TLC. Under aerobic conditions, no formation of the hydrazine was observed by HPLC and TLC examinations. However, when aerobic incubation was performed in the presence of acetaldehyde, a reduction product was isolated and identified as the acetaldehyde hydrazone derivative.
- Tatsumi,Yamada
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- Selective palladium-catalyzed arylation of ammonia: Synthesis of anilines as well as symmetrical and unsymmetrical di- and triarylamines
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It is shown that by selection of an appropriate palladium/ligand system, temperature, concentration, and stoichiometry of reagents, ammonia may be selectively arylated to give either anilines, symmetrical di-, or triarylamines. Furthermore different aryl halides may be added sequentially to the reaction mixture, allowing the synthesis of unsymmetrical di- and triarylamines from aryl halides and ammonia in a one-pot protocol Copyright
- Surry, David S.,Buchwald, Stephen L.
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- A novel organic electron donor derived from N-methylisatin
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We report the reactivity of an electron donor derived from N-methylisatin on reduction by sodium amalgam. Transfer of a clear supernatant solution to iodoarenes affords the products of two-electron reduction. Reductions of sulfones, activated arenesulfonamides, and Weinreb amides are also reported.
- Sword, Ryan,O'Sullivan, Steven,Murphy, John A.
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- Steric factors in the gas phase elimination kinetics of ethyl N-benzyl-N-cyclopropylcarbamate and ethyl diphenylcarbamate
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The elimination kinetics of ethyl N-benzyl-N-cyclopropylcarbamate and ethyl diphenylcarbamate were investigated over the temperature range of 349.9-440.0°C and the pressure range of 31-106 Torr. These reactions have been found to be homogeneous, unimolecular, and obey a first-order rate law. The products are ethylene, carbon monoxide, and the corresponding secondary amine. The rate coefficient is expressed by the following Arrhenius equations: For ethyl N-benzyl-N-cyclopropylcarbamate log k1 (s-1) = (1 2.94 ± 0.09) - (198.5 ± 0.9) kJ mol-1 (2.303RT)-1. For ethyl diphenylcarbamate log k1(S-1 = (12.91 ± 0.18) - (208.2 ± 2.4) kJ mol-1 (2.303RT)-1. The presence of phenyl and bulky groups at the nitrogen atom of the ethylcarbamate showed a decrease in the rate of elimination. Steric factor may be operating during the process of decomposition of these substrates. These reactions appear to undergo a semipolar six-membered cyclic transition type of mechanism.
- Luiggi,Dominguez,Rotinov,Herize,Cordova,Chuchani
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- Oxidation of Diphenylamine by OH Radicals and Excitation of the Diphenylamino and OH Adduct Radicals
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The primary product of the OH reaction with diphenylamine (DPAH) is a mixture of OH adducts (DPAH radical-OH) which subsequently eliminate OH- ions via a pH-independent and an acid-catalyzed process.The rate constants of these two processes have been determined.The acidic amino radical cation (DPAH+ radical) thus obtained has a pKa of 4.2.The adduct, the amino radical cation, and the neutral amino radical (DPA radical) were excited with frequency-doubled ruby laser pulses (347 nm).The excited state of the latter two amino radicals are shorter lived than the presently utilized laser pulse.Furthermore, no laser-induced shift in the acid-base equilibrium of DPAH+ radical/DPA radical could be observed.This lack of laser excitation effect leads to the conclusion that the difference in acid-base equilibrium constants (ΔpKa*) of the ground vs. the excited state is substantially smaller in the radical than in the analogous singlet states of the parent amine molecule.Foerster cycle considerations based on the absorption spectra of the two forms of the radical substantiate this conclusion.Excitation of the OH adduct leads to OH(1-) elimination from the excited state.This elimination leads to production of the amino radical cation in its ground state.Relaxation of this laser-induced perturbation of the acid-base equilibrium to its thermal value provides an independent method to measure the rates of equilibration.
- Schmidt, K. H.,Bromberg, A.,Meisel, Dan
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- Copper-Catalyzed Regioselective C-H Amination of Phenol Derivatives with Assistance of Phenanthroline-Based Bidentate Auxiliary
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A copper-catalyzed regioselective direct amination of phenol derivatives with diarylamines via phenanthroline-based bidentate auxiliary-directed C-H cleavage has been developed. This reaction proceeds smoothly with only a copper salt and air as a terminal oxidant to produce the corresponding o-aminophenols in good yields. Moreover, the directing group can be easily attached, detached, and recycled. Additionally, preliminary computational studies of the reaction with DFT have also been performed.
- Takamatsu, Kazutaka,Hayashi, Yoshihiro,Kawauchi, Susumu,Hirano, Koji,Miura, Masahiro
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- Potassium tert-butoxide-mediated generation of arynes from o-bromoacetophenone derivatives
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o-bromoacetophenone derivatives as new versatile aryne precursors are induced to selectively eliminate the CAr–Br and CAr–C(Ac) bonds in the help of t-BuOK. Furthermore, the active aryne intermediates are successfully appl
- Chang, Denghu,Gao, Fei,Shi, Lei
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- Preparation and characterization of Cu supported on 2-(1H-benzo[d]imidazol-2-yl)aniline-functionalized Fe3O4 nanoparticles as a novel magnetic catalyst for Ullmann and Suzuki cross-coupling reactions
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Copper supported on 2-(1H-benzo[d]imidazol-2-yl)aniline (BIA)-functionalized Fe3O4 nanoparticles (Cu-BIA-Si-Fe3O4) as a novel magnetic catalyst was designed and used for the synthesis of new products via Ullmann and Suzuki cross-coupling reactions. The Ullmann reaction was performed by mixing arylboronic acid with aniline derivatives in dimethylsulfoxide solvent. Also, diaryls were synthesized via Suzuki C–C reactions between aryl halides and phenylboronic acid in the same solvent. The prepared materials and catalyst were characterized with various analytical techniques. The Cu-BIA-Si-Fe3O4 catalyst demonstrated catalytic efficiency with good to excellent yields for both types of reactions in comparison with commercial palladium catalysts. Also, the catalyst could be recovered by a simple filtration and retained its activity even after several cycles.
- Danqing, Liang,Ming, Jin,Li, Li,Mohammadnia, Majid
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- The Quest for the Ideal Base: Rational Design of a Nickel Precatalyst Enables Mild, Homogeneous C-N Cross-Coupling
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Palladium-catalyzed amination reactions using soluble organic bases have provided a solution to the many issues associated with heterogeneous reaction conditions. Still, homogeneous C-N cross-coupling approaches cannot yet employ bases as weak and economical as trialkylamines. Furthermore, organic base-mediated methods have not been developed for Ni(0/II) catalysis, despite some advantages of such systems over those employing Pd-based catalysts. We designed a new air-stable and easily prepared Ni(II) precatalyst bearing an electron-deficient bidentate phosphine ligand that enables the cross-coupling of aryl triflates with aryl amines using triethylamine (TEA) as base. The method is tolerant of sterically congested coupling partners, as well as those bearing base- and nucleophile-sensitive functional groups. With the aid of density functional theory (DFT) calculations, we determined that the electron-deficient auxiliary ligands decrease both the pKa of the Ni-bound amine and the barrier to reductive elimination from the resultant Ni(II)-amido complex. Moreover, we determined that the preclusion of Lewis acid-base complexation between the Ni catalyst and the base, due to steric factors, is important for avoiding catalyst inhibition.
- Liu, Richard Y.,Dennis, Joseph M.,Buchwald, Stephen L.
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- Probing Hydrogen Atom Transfer at a Phosphorus(V) Oxide Bond Using a "bulky Hydrogen Atom" Surrogate: Analogies to PCET
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Recent computational studies suggest that the phosphate support in the commercial vanadium phosphate oxide (VPO) catalyst may play a critical role in initiating butane C-H bond activation through a mechanism termed reduction-coupled oxo activation (ROA) similar to proton-coupled electron transfer (PCET); however, no experimental evidence exists to support this mechanism. Herein, we present molecular model compounds, (Ph2N)3V=N-P(O)Ar2 (Ar = C6F5 (2a), Ph (2b)), which are reactive to both weak H atom donors and a Me3Si? (a "bulky hydrogen atom" surrogate) donor, 1,4-bis(trimethylsilyl)pyrazine. While the former reaction led to product decomposition, the latter resulted in the isolation of the reduced, silylated complexes (Ph2N)3V-N=P(OSiMe3)Ar2 (3a/b). Detailed analyses of possible reaction pathways, involving the isolation and full characterization of potential stepwise square-scheme intermediates, as well as the determination of minimum experimentally and computationally derived thermochemical values, are described. We find that stepwise electron transfer (ET) + silylium transfer (ST) or concerted EST mechanisms are most likely. This study provides the first experimental evidence supporting a ROA mechanism and may inform future studies in homogeneous or heterogeneous C-H activation chemistry, as well as open up a possible new avenue for main group/transition metal cooperative redox reactivity.
- Chu, Jiaxiang,Carroll, Timothy G.,Wu, Guang,Telser, Joshua,Dobrovetsky, Roman,Ménard, Gabriel
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- Scalable production of Cu@C composites for cross-coupling catalysis
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A novel Cu@C core-shell microstructure was prepared by reduction of [Cu(NH3)4]2+ with glucose using a mild hydrothermal process. The carbon shell of such Cu@C composite can be tuned to different carbonization degrees just through varying the calcination conditions. The structural properties of as-prepared Cu@C were investigated in detail by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron micrographs (TEM) and Raman spectra. In addition, these Cu@C composites were firstly used to catalyze the CN cross coupling of amines with iodobenzene. Among them, the catalytic ability of Cu@C composites increased as their surface carbon's carburization degree improved.
- Bu, Lijuan,Ming, Hai
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- Magnetic acyclovir-copper nanoparticle: DFT study and application as an efficient, magnetically separable and recyclable catalyst for N-arylation of amines under green condition
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A copper(I)‐acyclovir complex supported on magnetic was designed and successfully synthesized. Catalytic activity and stability of two structures of copper(I)‐acyclovir complex supported on magnetic were investigated by the theoretical method. The more active and stable copper(I)‐acyclovir complex supported on magnetic was applied as a catalyst for C–N cross‐coupling reaction with high yield in a deep eutectic solvent (DES) as a green solvent. Also, these nanoparticles could be easily recovered and reused for new rounds of reaction without any considerable loss in catalytic activity.
- Heydari, Akbar,Pazoki, Farzane
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- Well-defined copper(I) amido complex and aryl iodides reacting to form aryl amines
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The CuI complex (IPr)Cu(NHPh) {IPr = 1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene} reacts with aryl iodides to form diaryl amine products and (IPr)Cu(I), which was confirmed by independent synthesis and characterization. For the reaction with iodobenzene, the products are diphenylamine and aniline. Protection of the hydrogen para to the iodo functionality with ortho-methyl groups results in quantitative conversion to diaryl amine. Combined computational and experimental studies suggest that C-N bond formation most likely occurs via an oxidative addition/reductive elimination sequence.
- Delp, Samuel A.,Goj, Laurel A.,Pouy, Mark J.,Munro-Leighton, Colleen,Lee, John P.,Gunnoe, T. Brent,Cundari, Thomas R.,Petersen, Jeffrey L.
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- PHOTOCHEMISTRY OF 1,3-DIPHENYLTRIAZENE IN VARIOUS MEDIA. I: PHOTOLYSIS IN LIQUID SOLUTIONS.
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1,3-Diphenyltriazene has been irradiated at 360 nm in various liquid solutions. Reversible trans-cis photoisomerization has been detected in solvents which do not form hydrogen bonds. Irreversible photolysis is observed with an appreciable amount of cage recombination products in all solvents. This reaction is well suited for a study in solid environments.
- Baro,Dudek,Luther,Troe
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- Reduction of nitroarenes, azoarenes and hydrazine derivatives by an organic super electron donor
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Reduction of nitrobenzene by excess organic electron donor, 12, affords diphenylhydrazine in a reaction where azobenzene oxide and azobenzene are likely intermediates. No cleavage of the N-N σ-bond is seen under photoactivation conditions, whereas traces are seen under thermal activation. Hydrazone derivatives were prepared to explore the cleavage of N-N σ-bonds; the results show that a low-lying LUMO assists the transition state for accepting an electron, and the stabilisation that the potential fragments from N-N bond cleavage afford to the fragments is important in determining whether cleavage is observed.
- Cumine, Florimond,Palumbo, Fabrizio,Murphy, John A.
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- Room-temperature palladium-catalyzed amination of aryl bromides and chlorides and extended scope of aromatic C-N bond formation with a commercial ligand
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The reactions of aryl bromides with amines occurs at room temperature when using Pd(0) and P(t-Bu)3 in a 1:1 ratio, and the reactions of aryl chlorides occur at room temperature or 70 °C. The arylation of indoles and the new arylation of carbamates also occur when using P(t-Bu)3 as ligand.
- Hartwig, John F.,Kawatsura, Motoi,Hauck, Sheila I.,Shaughnessy, Kevin H.,Alcazar-Roman, Luis M.
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- Cu(II)-Catalyzed Ortho C(sp2)-H Diarylamination of Arylamines to Synthesize Triarylamines
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A copper-catalyzed, directed ortho C-H diarylamination of indoles, indolines, anilines, and N-aryl-7-azaindoles has been established. Only copper salt as the catalyst and oxygen as the terminal oxidant are used to synthesize triarylamines using various diarylamines including carbazole and phenothiazine. Mechanistic interrogation reveals that copper plays a dual role.
- Ahmad, Ashfaq,Dutta, Himangsu Sekhar,Khan, Afsar Ali,Koley, Dipankar,Kumar, Mohit,Raziullah,Sharma, Rishabh
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- Low-valent titanium mediated deprotection of N-allyl/benzyl amines: A new approach
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A novel low-valent titanium (LVT) mediated cleavage of N-allyl/benzyl amines is reported. Regio- and chemo-selective cleavages were also observed.
- Talukdar,Banerji
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- Highly active salted low-valent titanium reagents for various SET induced reactions
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External addition of inorganic salts (Group I and II metal halides) to the preformed low-valent titanium reagent A (TiCl3-Li-THF) dramatically enhanced its activity. The new reagents were used to carry out various SET reactions including McMurry's olefination at a faster rate even at ambient temperature.
- Rele, Shyam,Chattopadhyay, Subrata,Nayak, Sandip K.
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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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supporting information
(2022/03/15)
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- CO2-tuned highly selective reduction of formamides to the corresponding methylamines
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We herein describe an efficient, CO2-tuned and highly selective C-O bond cleavage of N-methylated formanilides. With easy-to-handle and commercially available NaBH4 as the reductant, a variety of formanilides could be turned into the desired tertiary amines in moderate to excellent yields. The role of CO2 has been investigated in detail, and the mechanism is proposed on the basis of experiments.
- Chao, Jianbin,Guo, Zhiqiang,Pang, Tengfei,Wei, Xuehong,Xi, Chanjuan,Yan, Leilei
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supporting information
p. 7534 - 7538
(2021/10/12)
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- Method for protecting sulfonyl of deamination amine
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The invention discloses a method for removing sulfenyl protection of amine. The method comprises the following steps: dissolving N - sulfonyl-protected amine and a base in a reaction solvent, then adding diphenylphosphine to uniformly mix and maintain 90 °C. When TCL detection reaction is complete, a recrystallization method or an extraction separation method is adopted to obtain the target product. The method disclosed by the invention adopts diphenylphosphine as an extraction reagent, is good in reaction activity, high in selectivity and wide in application range, and can replace the use of a hazardous reagent under the basic heating condition. Prodrug research and development and industrial production are of great significance.
- -
-
Paragraph 0039-0041
(2021/11/03)
-
- A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions
-
A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.
- Huang, Binbin,Guo, Lin,Xia, Wujiong
-
supporting information
p. 2095 - 2103
(2021/03/26)
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- Radical Chain Reduction via Carbon Dioxide Radical Anion (CO2?-)
-
We developed an effective method for reductive radical formation that utilizes the radical anion of carbon dioxide (CO2?-) as a powerful single electron reductant. Through a polarity matched hydrogen atom transfer (HAT) between an electrophilic radical and a formate salt, CO2?- formation occurs as a key element in a new radical chain reaction. Here, radical chain initiation can be performed through photochemical or thermal means, and we illustrate the ability of this approach to accomplish reductive activation of a range of substrate classes. Specifically, we employed this strategy in the intermolecular hydroarylation of unactivated alkenes with (hetero)aryl chlorides/bromides, radical deamination of arylammonium salts, aliphatic ketyl radical formation, and sulfonamide cleavage. We show that the reactivity of CO2?- with electron-poor olefins results in either single electron reduction or alkene hydrocarboxylation, where substrate reduction potentials can be utilized to predict reaction outcome.
- Hendy, Cecilia M.,Jui, Nathan T.,Lian, Tianquan,Smith, Gavin C.,Xu, Zihao
-
supporting information
p. 8987 - 8992
(2021/07/01)
-
- Organic compound and electronic component and electronic device comprising same
-
The invention provides an organic compound and an electronic element and an electronic device comprising the same, and belongs to the technical field of organic electroluminescence. The structural formula of the organic compound is composed of a structure as shown in a chemical formula 1, and the organic compound has excellent photoelectric properties, can improve the luminous efficiency and the service life of the device, and can reduce the working voltage.
- -
-
Paragraph 0113-0115; 0116-0118; 0119
(2021/07/17)
-
- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING SAME AND ELECTRONIC DEVICE THEREFOR
-
Disclosed is a compound represented by chemical formula (1). In addition, disclosed is an organic electronic element comprising: a first electrode; a second electrode; and an organic layer between the first electrode and the second electrode, wherein the organic layer contains the compound represented by chemical formula (1). Light-emitting efficiency, stability and lifespan may be enhanced when the compound represented by chemical formula (1) is contained in the organic layer.
- -
-
Paragraph 0106-0107; 0118-0119
(2021/10/02)
-
- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF
-
The compound is represented by chemical formula 1. 1 Is a cross-sectional view of an organic electronic device including an organic material layer between the first electrode, the first 2 electrode and the first 1 electrode, and 2. A compound represented by Formula 1 is included in the organic material layer, thereby decreasing a driving voltage of the organic electronic device and improving light emitting efficiency and lifespan.
- -
-
Paragraph 0113-0116; 0155-0158
(2021/10/19)
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- Triarylamine derivative and organic electroluminescent device thereof
-
The invention provides a triarylamine derivative and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescence. The triarylamine derivative provided by the invention has a higher triplet energy level. When the organic electroluminescent device is applied to the organic electroluminescent device, the driving voltage of the organic electroluminescent device can be effectively reduced, the luminous efficiency is improved, and the service life of the device is prolonged.
- -
-
Paragraph 0179-0182; 0231-0233
(2021/09/15)
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- Fe-MIL-101 modified by isatin-Schiff-base-Co: a heterogeneous catalyst for C-C, C-O, C-N, and C-P cross coupling reactions
-
A metal-organic framework functionalized with a cobalt-complex is preparedviapost-synthetic modification of Fe-MIL-101-NH2. Initially, Fe-MIL-101-NH2reacted with isatin to produce Fe-MIL-101-isatin-Schiff-base, which can anchor the cobalt by the addition of cobalt acetate. The resulting MOF-Co catalyst is characterized by employing multiple techniques. This new modified MOF acts as a heterogeneous and recyclable catalyst for efficient Ullmann, Buchwald-Hartwig, Hirao, Hiyama and Mizoroki-Heck cross-coupling reactions of several aryl halides/phenylboronic acid/phenyltosylate with phenols, anilines/heterocyclic amines, triethyl phosphite, triethoxyphenylsilane and alkenes and generates the expected coupling products in good to high yields.
- Farrokhi, Alireza,Rouzifar, Majid,Sansano, José Miguel,Sobhani, Sara
-
p. 19963 - 19976
(2021/11/12)
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- Schiff bases-titanium (III) & (IV) complex compounds: Novel photocatalysts in Buchwald-Hartwig C–N cross-coupling reaction
-
Nine novel Schiff bases were derived from salicylic aldehyde and oxalic aldehyde, isolated, and their molecular and spatial structure were explored by a set of experiments (IR, CNMR, HNMR, CHN, SEM, XRD) and theoretical simulation (DFT def2-TZVP). A high potential was predicted in metal cations chelating. The isolated organic species were applied as the ligands in the reaction of complex formation with titanium (III) chloride and (IV) bromide and 12 novel complexes were synthesized and studied experimentally and theoretically. Using the UV–vis spectroscopic titration, the solution stability of the complexes was indicated. Depending on the nature of the Schiff base ligand, their formation constants were calculated in the range of 6.84–17.32. Using the DFT def2-TZVP theoretical method together with the experimental spectroscopic data, the coordination types of the ligands were investigated, and the structure of the complexes was proposed. The photocatalytic ability of the isolated complexes was tested in the C-N cross-coupling reaction under sunlight. Complexes exhibited high visible-light photocatalytic activity for a wide range of aromatic and benzylic amines including electron-withdrawing and electron-donating groups from moderate to good yields ranging in 50–85 %. The use of an inexpensive, clean, and renewable energy source (visible light) is the superiority of the developed photocatalytic systems.
- Absalan, Yahya,Ghandi, Khashayar,Gholizadeh, Mostafa,Kovalchukova, Olga,Mahmoudi, Ghodrat,Sarvestani, Hossein Sabet,Shad, Nazanin Noroozi,Strashnov, Pavel
-
-
- Diamine derivative and organic electroluminescent device thereof
-
The invention provides a diamine derivative and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescent materials. The diamine derivative represented by Formula 1 contains 9 -fluorene-substituted carbazole functional group, and the hole transport region or cover layer of the organic electroluminescent device of the present invention contains the carbazole derivative of Formula 1. The diamine derivative represented by the formula 1 has better hole transport performance and stability, and the prepared organic electroluminescent device containing the diamine derivative of the formula 1 in the prepared hole transport region exhibits high luminous efficiency. A longer service life and is a lower driving voltage. In addition, the diamine derivative of the formula 1 is also a better cover layer material; the prepared cover layer contains the diamine derivative of the formula 1; the organic electroluminescent device has high luminous efficiency and long service life.
- -
-
Paragraph 0121-0122; 0128-0129
(2021/12/07)
-
- Nitrogen-containing compound, organic electroluminescent device, and electronic device
-
The invention provides a nitrogen-containing compound, an organic electroluminescent device and an electronic device, and belongs to the technical field of organic materials. The structure of the nitrogen-containing compound is represented by Chemical Formula 1: wherein X1, X2, Y1, Y2 are the same or different from each other and are each independently a single bond, O, S, N(R3), C(R4R5), Ge(R6R7), Si(R8R9), Se, wherein X1 and Y1 are not single bonds simultaneously and X2 and Y2 are not single bonds simultaneously.
- -
-
Paragraph 0111-0114
(2021/01/24)
-
- L-Proline N-oxide dihydrazides as an efficient ligand for cross-coupling reactions of aryl iodides and bromides with amines and phenols
-
A novel catalytic system based on L-proline N-oxide/CuI was developed and applied to the cross-coupling reactions of various N- and O- nucleophilic reagents with aryl iodides and bromides. This strategy featured in the employment of an-proline derived dihydrazides N-oxide compound as the superior supporting ligand. By using this protocol, a variety of products, including N-arylimidazoles, N-arylpyrazoles, N-arylpyrroles, N-arylamines, and aryl ethers, were synthesized with up to 99% yield.
- Ding, Zhiqiang,Nie, Nan,Chen, Tian,Meng, Lingxin,Wang, Gongshu,Chen, Zhangpei,Hu, Jianshe
-
supporting information
(2020/12/21)
-
- Copper nanoparticle anchored biguanidine-modified Zr-UiO-66 MOFs: a competent heterogeneous and reusable nanocatalyst in Buchwald-Hartwig and Ullmann type coupling reactions
-
We have designed a functionalized metal-organic framework (MOF) of UiO topology as a support, with an extremely high surface area, adjustable pore sizes and stable crystalline coordination polymeric structure and implanted copper (Cu) nanoparticles thereon. The core three dimensional Zr-derived MOF (UiO-66-NH2) was modified with a biguanidine moiety following a covalent post-functionalization approach. The morphological and physicochemical features of the material were determined using analytical methods such as FT-IR, SEM, TEM, EDX, atomic mapping, XRD and ICP-OES. The SEM and XRD results justified the unaffected morphology of Zr-MOF after structural modifications. The as-synthesized UiO-66-biguanidine/Cu nanocomposite was catalytically explored in the aryl and heteroaryl Buchwald-Hartwig C-N and Ullmann type C-O cross coupling reactions with excellent yields. A library of biaryl amine and biaryl ethers was synthesized over the catalyst under mild and green conditions. Furthermore, the catalyst was isolated by centrifugation and recycled 11 times with no significant copper leaching or change in its activity.
- Veisi, Hojat,Neyestani, Narges,Pirhayati, Mozhgan,Ahany Kamangar, Sheida,Lotfi, Shahram,Tamoradi, Taiebeh,Karmakar, Bikash
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p. 22278 - 22286
(2021/07/02)
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- Effect of Precatalyst Oxidation State in C-N Cross-Couplings with 2-Phosphinoimidazole-Derived Bimetallic Pd(I) and Pd(II) Complexes
-
We report the catalytic activity of two phosphinoimidazole-derived bimetallic palladium complexes in Pd-catalyzed amination reactions. Our studies demonstrate that the starting oxidation state (Pd(I) or Pd(II)) of the dimeric complex has a significant effect on the efficiency of the catalytic reaction. The corresponding Pd(I) complex shows higher reactivity in Buchwald-Hartwig aminations, while the Pd(II) complex is much more reactive in carbonylative amination reactions. These new dimeric palladium complexes provide good to excellent reactivity and yields in the amination reactions tested.
- Martinez, Erin E.,Moreno, Mariur Rodriguez,Barksdale, Caleb A.,Michaelis, David J.
-
supporting information
p. 2763 - 2767
(2021/08/27)
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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
-
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
-
-
- Cu(I)–N-heterocyclic carbene-catalyzed base free C–N bond formation of arylboronic acids with amines and azoles
-
A new N-heterocyclic carbene (NHC) precursor of imidazolium chloride and its corresponding Cu(I)–NHC complex 1 was synthesized. The complex 1 was found to be a highly effective catalyst for Chan-Evans-Lam coupling of arylboronic acid with amines and azoles (including imidazole, pyrazole and triazole), without addition of base at room temperature. Various substituents on three substrates can be tolerated, giving the desired coupling products in good to excellent yields (62–94%). The method is practical and offers an alternative to the corresponding copper-catalyzed Chan-Evans-Lam process for the construction of C–N bonds.
- Zhang, Maoyuan,Xu, Zengbing,Shi, Dabin
-
-
- Mediator-Enabled Electrocatalysis with Ligandless Copper for Anaerobic Chan-Lam Coupling Reactions
-
Simple copper salts serve as catalysts to effect C-X bond-forming reactions in some of the most utilized transformations in synthesis, including the oxidative coupling of aryl boronic acids and amines. However, these Chan-Lam coupling reactions have historically relied on chemical oxidants that limit their applicability beyond small-scale synthesis. Despite the success of replacing strong chemical oxidants with electrochemistry for a variety of metal-catalyzed processes, electrooxidative reactions with ligandless copper catalysts are plagued by slow electron-transfer kinetics, irreversible copper plating, and competitive substrate oxidation. Herein, we report the implementation of substoichiometric quantities of redox mediators to address limitations to Cu-catalyzed electrosynthesis. Mechanistic studies reveal that mediators serve multiple roles by (i) rapidly oxidizing low-valent Cu intermediates, (ii) stripping Cu metal from the cathode to regenerate the catalyst and reveal the active Pt surface for proton reduction, and (iii) providing anodic overcharge protection to prevent substrate oxidation. This strategy is applied to Chan-Lam coupling of aryl-, heteroaryl-, and alkylamines with arylboronic acids in the absence of chemical oxidants. Couplings under these electrochemical conditions occur with higher yields and shorter reaction times than conventional reactions in air and provide complementary substrate reactivity.
- Walker, Benjamin R.,Manabe, Shuhei,Brusoe, Andrew T.,Sevov, Christo S.
-
supporting information
p. 6257 - 6265
(2021/05/07)
-
- Cu(OAc)2-porphyrins as an efficient catalytic system for base-free, nature mimicking Chan–Lam coupling in water
-
The use of porphyrins as ligands in organic synthesis reveals the natural process, because these are the constituent motifs of catalysts in many bio-organic reactions. This article presents the synthesis of two N-pincer tetradentate porphyrins; tetrasodium meso-tetra(p-sulfonatophenyl)phorphyrin (H2TSTpSPP) and meso-tetra(m-carboxyphenyl)porphyrin (H2TmCPP), and study on their aptness for Cu-catalyzed C–N coupling reactions of arylboronic acids and amines (Chan–Lam coupling reaction) in water under external base free conditions. The porphyrins and Chan–Lam coupling products were well characterized by their spectral analysis. The high product yields, application of nature-inspired conditions, large extent of substrates, ease of making and handling the ligands, avoidance of base, and use of water as reaction media are the attractive attributes of this finding.
- Venkateswarlu, Katta,Rao, Kanusu Umamaheswara
-
-
- NaOTs-promoted transition metal-free C-N bond cleavage to form C-X (X = N, O, S) bonds
-
Multifunctional transformation of amide C-N bond cleavage is reported. The protocol applies to benzamide, thioamide, alcohols, and mercaptan under similar reaction conditions catalyzed by NaOTs. It is noteworthy that NaOTs can not only be recycled and reused for up to three cycles without significant loss in catalytic activity, but also catalyze gram-grade reactions. This study provides a novel solution with mild conditions and a simple procedure for transformation of multiple amides.
- Chen, Wei,Liu, Sicheng,Liu, Tingting,Majeed, Irfan,Ye, Xiaojing,Zeng, Zhuo,Zhang, Yuqi,Zhu, Yulin
-
supporting information
p. 8566 - 8571
(2021/10/20)
-
- N-Heterocyclic Carbene Palladium(II) Amine Complexes: The Role of Primary Aryl- or Alkylamine Binding and Applications in the Buchwald-Hartwig Amination Reaction
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N-heterocyclic carbene-palladium(II) amine complexes bearing primary aryl- or alkylamines were synthesized. The prepared complexes were characterized by single crystal X-ray diffraction as well as NMR spectroscopy. These complexes exhibited good catalytic activities for the Buchwald-Hartwig amination reaction of aryl chlorides to afford arylated anilines under mild conditions. All reactions were carried out in air and all starting materials were used as supplied without purification. 21 expected coupling products were obtained in moderate to high yields under optimum conditions.
- Chen, Ming-Tsz,Hsu, Yu-Cheng
-
supporting information
(2021/12/24)
-
- A quinoxaline-based porous organic polymer containing copper nanoparticles CuNPs@Q-POP as a robust nanocatalyst toward C-N coupling reaction
-
A novel porous organic polymer (denoted by Q-POP) was successfully fabricated by free-radical copolymerization of allyl-substituted 2,3-di(2-hydroxyphenyl)1,2-dihydroquinoxaline, and divinylbenzene under solvothermal conditions and used as a new platform for immobilization of copper nanoparticles. The CuNPs@Q-POP nanocatalyst was prepared via incorporating of Cu(NO3)2 into the polymeric network, followed by the reduction of Cu2+ ion with hydrazine hydrate. The obtained materials were characterized through FT-IR, XRD, N2 adsorption-desorption isotherms, ICP, TGA, SEM, HR-TEM, EDX, and the single-crystal X-ray crystallography. The results displayed that Q-POP and CuNPs@Q-POP possessed high surface area, hierarchical porosity, and excellent thermal and chemical stability. The as-synthesized catalyst was utilized for the Ullmann C-N coupling reaction of aromatic amines and different aryl halides to prepare various diarylamine derivatives. All types of aryl halides (except aryl fluorides) were screened in the Ullmann C-N coupling reaction with aromatic amines to produce diaryl amines in good to excellent yields (50-98%), and it turned out that aryl iodides have the best results. Besides, due to the strong interactions between CuNPs, N, and O-atoms of quinoxaline moiety existing in the polymeric framework, the copper leaching from the support was not observed. Furthermore, the catalyst was recycled and reused for five consecutive runs without significant activity loss.
- Gorginpour, Forough,Zali-Boeini, Hassan,Rudbari, Hadi Amiri
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p. 3655 - 3665
(2021/02/03)
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- Preparation method of secondary aromatic amine
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The invention provides a method for preparing secondary aromatic amine by performing a palladium-catalyzed C-N coupling reaction on (pseudo)aryl halide and (pseudo)heterocyclic aryl halide and primary(heterocyclic)aromatic amine. The method is characterized in that an alkali for promoting the reaction is an alkali metal carboxylate or an alkali metal bicarbonate.
- -
-
Paragraph 0023-0024
(2021/03/31)
-
- Method for synthesizing diarylamine through N-arylation reaction of arylamine under copper catalysis
-
The invention provides a method for synthesizing diarylamine through an N-arylation reaction of arylamine under copper catalysis. The method comprises the following steps: S1, selecting a proper amount of a reaction reagent, a catalyst, a solvent and the like; S2, sequentially adding a reaction reagent, a catalyst, a solvent and the like into a reaction tube with a magnetic bar; S3, selecting a proper amount of AcOH, and adding the AcOH into the reaction tube; S4, heating the reaction tube; S5, performing oil bath treatment; S6, cooling to room temperature, and diluting; S7, extracting by using ethyl acetate; S8, washing the organic layer with saline water; S9, drying on anhydrous Na2SO4; S10, evaporating under vacuum; and S11, purifying the residues into the pure product through silica gel chromatography. A scheme that arylamine and an environmentally-friendly and stable aryl silicon reagent are subjected to an N-arylation reaction under the catalysis of a cheap copper reagent is provided, Cu(OAc)2 is used as a catalyst to react in DMSO in the atmosphere of O2, the conversion reactivity is good, the substrate range is wide, and the method has good tolerance to reaction substrates with various functional groups under mild reaction conditions.
- -
-
Paragraph 0082; 0083
(2021/07/14)
-
- Electron Push-Pull Effects on Intramolecular Charge Transfer in Perylene-Based Donor-Acceptor Compounds
-
A series of asymmetric donor-acceptor (D-A) perylene-based compounds, 3-(N,N-bis(4′-(R)-phenyl)amino)perylene (Peri-DPA(R)), were successfully prepared to explore their intramolecular charge transfer (ICT) properties. To induce ICT between the donor and acceptor, diphenylamine (DPA) derivatives (electron donor units) with the same functional groups (R = CN, F, H, Me, or OMe) at both para positions were linked to the C-3 position of perylene to produce five Peri-DPA derivatives. A steady-state spectroscopy study on Peri-DPA(R)s exhibited a progressively regulated ICT trend consistent with the substituent effect as it progressed from the electron-withdrawing group to the electron-donating group. In particular, a comparative study using a D-A-D (donor-acceptor-donor) system demonstrated that not only the electron push-pull substituent effect but also subunit combinations influence photophysical and electrochemical properties. The different ICT characters observed in Lippert-Mataga plots of D-A(CN) and D-A-D(CN) (CN-substituted D-A and D-A-D) led to the investigation on whether ICT emission of two systems with differences in subunit combinations is of the same type or of a different type. The femtosecond transient absorption (fs-TA) spectroscopic results provided direct evidence of ICT origin and confirmed that D-A(CN) and D-A-D(CN) exhibited the same transition mix of ICT (from donor to acceptor) and reverse ICT (rICT, from arylamine to CN unit). Density functional theory (DFT)/TD-DFT calculations support the presence of ICT for all five compounds, and the experimental observations of rICT presented only for CN-substituted compounds.
- Ahn, Mina,Kim, Min-Ji,Cho, Dae Won,Wee, Kyung-Ryang
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p. 403 - 413
(2020/12/23)
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- Synthesis of Substituted Anilines from Cyclohexanones Using Pd/C-Ethylene System and Its Application to Indole Synthesis
-
The synthesis of anilines and indoles from cyclohexanones using a Pd/C-ethylene system is reported. A simple combination of NH4OAc and K2CO3 under nonaerobic conditions was found to be the most suitable to perform this reaction. Hydrogen transfer between cyclohexanone and ethylene generates the desired products. The reaction tolerates a variety of substitutions on the starting cyclohexanones.
- Maeda, Katsumi,Matsubara, Ryosuke,Hayashi, Masahiko
-
supporting information
p. 1530 - 1534
(2021/03/08)
-
- Electrochemical Reductive Arylation of Nitroarenes with Arylboronic Acids
-
The synthesis of diarylamine is extremely important in organic chemistry. Herein, a novel electrochemical reductive arylation of nitroarenes with arylboronic acids was developed. A variety of diarylamines were synthesized without the need for transition-metal catalysts. The reaction could be scaled up efficiently in a flow cell and several derivatization reactions were carried out smoothly. Cyclic voltammetry experiments and mechanism studies showed that acetonitrile, formic acid, and triethyl phosphite all played a role in promoting this reductive arylation transformation.
- Wang, Dan,Wan, Zhaohua,Zhang, Heng,Alhumade, Hesham,Yi, Hong,Lei, Aiwen
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p. 5399 - 5404
(2021/10/20)
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- Nickel-Catalyzed Amination of Aryl Chlorides with Amides
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A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.
- Li, Jinpeng,Huang, Changyu,Wen, Daheng,Zheng, Qingshu,Tu, Bo,Tu, Tao
-
supporting information
p. 687 - 691
(2021/01/09)
-
- Indirect reduction of CO2and recycling of polymers by manganese-catalyzed transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes
-
The reduction of polar bonds, in particular carbonyl groups, is of fundamental importance in organic chemistry and biology. Herein, we report a manganese pincer complex as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and even polyurethanes leading to the corresponding alcohols, amines, and methanol as products. Since these compound classes can be prepared using CO2as a C1 building block the reported reaction represents an approach to the indirect reduction of CO2. Notably, these are the first examples on the reduction of carbamates and urea derivatives as well as on the C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is highlighted by the successful reduction of 12 urea derivatives, 26 carbamates and 11 amides. The corresponding amines, alcohols and methanol were obtained in good to excellent yields up to 97%. Furthermore, polyurethanes were successfully converted which represents a viable strategy towards a circular economy. Based on control experiments and the observed intermediates a feasible mechanism is proposed.
- Liu, Xin,Werner, Thomas
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p. 10590 - 10597
(2021/08/20)
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- Visible-Light- And PPh3-Mediated Direct C-N Coupling of Nitroarenes and Boronic Acids at Ambient Temperature
-
We present here a metal-free, visible-light- and triphenylphosphine-mediated intermolecular, reductive amination between nitroarenes and boronic acids at ambient temperature without any photocatalyst. Mechanistically, a slow reduction of nitroarenes to a nitroso and, finally, a nitrene intermediate occurs that leads to the amination product with concomitant 1,2-aryl/-alkyl migration from a boronate complex. A wide range of nitroarenes underwent C-N coupling with aryl-/alkylboronic acids providing high yields.
- Manna, Kartic,Ganguly, Tanusree,Baitalik, Sujoy,Jana, Ranjan
-
supporting information
p. 8634 - 8639
(2021/11/01)
-
- Nickel-Catalyzed Amination of Aryl Nitriles for Accessing Diarylamines through C?CN Bond Activation
-
A nickel-catalyzed amination to access diarylamines has been developed through C?CN bond activation of aryl nitriles with anilines. In this developed catalytic protocol, various aromatic and heteroaromatic nitriles could be utilized as the electrophiles to couple with substituted anilines. A diversity of diarylamines were obtained in 15–95% yields. (Figure presented.).
- Wu, Ke,Rong, Qiang,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Jin, Liqun,Hu, Xinquan
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p. 4708 - 4713
(2021/08/27)
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- Sterically Stabilized End-On Superoxocopper(II) Complexes and Mechanistic Insights into Their Reactivity with O-H, N-H, and C-H Substrates
-
Instability of end-on superoxocopper(II) complexes, with respect to conversion to peroxo-bridged dicopper(II) complexes, has largely constrained their study to very low temperatures. This limits their kinetic capacity to oxidize substrates. In response, we have developed a series of bulky ligands, Ar3-TMPA (Ar = tpb, dpb, dtbpb), and used them to support copper(I) complexes that react with O2 to yield [CuII(?1-O2?-)(Ar3-TMPA)]+ species, which are stable against dimerization at all temperatures. Binding of O2 saturates at subambient temperatures and can be reversed by warming. The onset of oxygenation for the Ar = tpb and dpb systems is observed at 25 °C, and all three [CuII(?1-O2?-)(Ar3-TMPA)]+ complexes are stable against self-decay at temperatures of ≤-20 °C. This provides a wide temperature window for study of these complexes, which was exploited by performing extensive reaction kinetics measurements for [CuII(?1-O2?-)(tpb3-TMPA)]+ using a broad range of O-H, N-H, and C-H bond substrates. This includes correlation of second order rate constants (k2) versus oxidation potentials (Eox) for a range of phenols, construction of Eyring plots, and temperature-dependent kinetic isotope effect (KIE) measurements. The data obtained indicate that reaction with all substrates proceeds via H atom transfer (HAT), reaction with the phenols proceeds with significant charge transfer, and full tunneling of both H and D atoms occurs in the case of 1,2-diphenylhydrazine and 4-methoxy-2,6-di-tert-butylphenol. Oxidation of C-H bonds proved to be kinetically challenging, and whereas [CuII(?1-O2?-)(tpb3-TMPA)]+ can oxidize moderately strong O-H and N-H bonds, it is only able to oxidize very weak C-H bonds.
- Debnath, Suman,England, Jason,Kr?mer, Tobias,Laxmi, Shoba,Quek, Sebastian Y.,Van Gastel, Maurice
-
supporting information
p. 19731 - 19747
(2021/11/30)
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- A Novel Modified Cross-Coupling of Phenols and Amines Using Dichloroimidazolidinedione (DCID)
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Phenols are considered as an ideal alternative to aryl halides as coupling partners in cross-coupling reactions. In the present work a copper-catalyzed cross-coupling of phenols with various aromatic and aliphatic amines for the synthesis of secondary aryl amines using dichloroimidazolidinedione (DCID) as a new and efficient activating agent has been developed. Substituted phenols were compatible with the standard reaction conditions. The two proposed mechanisms, which are based on the oxidation addition of copper with Ar-OMCID (MCID: Monochloroimidazolidinedione), are also discussed.
- Madankar, Kamelia,Mokhtari, Javad,Mirjafary, Zohreh
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supporting information
p. 1725 - 1729
(2020/09/01)
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- Combined KOH/BEt3Catalyst for Selective Deaminative Hydroboration of Aromatic Carboxamides for Construction of Luminophores
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The selective catalytic C-N bond cleavage of amides into value-added amine products is a desirable but challenging transformation. Molecules containing iminodibenzyl motifs are prevalent in pharmaceutical molecules and functional materials. Here we established a combined KOH/BEt3 catalyst for deaminative hydroboration of acyl-iminodibenzyl derivatives, including nonheterocyclic carboxamides, to the corresponding amines. This novel transition-metal-free methodology was also applied to the construction of Clomipramine and luminophores.
- Li, Jinshan,Wang, Jiali,Yang, Jianguo,Yao, Wubing,Zhong, Aiguo
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p. 8086 - 8090
(2020/11/03)
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- Synthesis of unsymmetrically substituted triarylaminesviaacceptorless dehydrogenative aromatization using a Pd/C andp-toluenesulfonic acid hybrid relay catalyst
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An efficient and convenient procedure for synthesizing triarylamines based on a dehydrogenative aromatization strategy has been developed. A hybrid relay catalyst comprising carbon-supported Pd (Pd/C) andp-toluenesulfonic acid (TsOH) was found to be effective for synthesizing a variety of triarylamines bearing different aryl groups starting from arylamines (diarylamines or anilines), using cyclohexanones as the arylation sources under acceptorless conditions with the release of gaseous H2. The proposed reaction comprises the following relay steps: condensation of arylamines and cyclohexanones to produce imines or enamines, dehydrogenative aromatization of the imines or enamines over Pd nanoparticles (NPs), and elimination of H2from the Pd NPs. In this study, an interesting finding was obtained indicating that TsOH may promote the dehydrogenation.
- Jin, Xiongjie,Koizumi, Yu,Mizuno, Noritaka,Nozaki, Kyoko,Takayama, Satoshi,Yamaguchi, Kazuya,Yatabe, Takafumi
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p. 4074 - 4084
(2020/05/25)
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- Transition-Metal-Free and Visible-Light-Mediated Desulfonylation and Dehalogenation Reactions: Hantzsch Ester Anion as Electron and Hydrogen Atom Donor
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Novel approaches for N- and O-desulfonylation under room temperature (rt) and transition-metal-free conditions have been developed. The first methodology involves the transformation of a variety of N-sulfonyl heterocycles and phenyl benzenesulfonates to the corresponding desulfonylated products in good to excellent yields using only KOtBu in dimethyl sulfoxide (DMSO) at rt. Alternately, a visible light method has been used for deprotection of N-methyl-N-arylsulfonamides with Hantzsch ester (HE) anion serving as the visible-light-absorbing reagent and electron and hydrogen atom donor to promote the desulfonylation reaction. The HE anion can be easily prepared in situ by reaction of the corresponding HE with KOtBu in DMSO at rt. Both protocols were further explored in terms of synthetic scope as well as mechanistic aspects to rationalize key features of desulfonylation processes. Furthermore, the HE anion induces reductive dehalogenation reaction of aryl halides under visible light irradiation.
- Heredia, Micaela D.,Guerra, Walter D.,Barolo, Silvia M.,Fornasier, Santiago J.,Rossi, Roberto A.,Budén, Mariá E.
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supporting information
p. 13481 - 13494
(2020/12/15)
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- Protocol for Visible-Light-Promoted Desulfonylation Reactions Utilizing Catalytic Benzimidazolium Aryloxide Betaines and Stoichiometric Hydride Donor Reagents
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An unprecedented photocatalytic system consisting of benzimidazolium aryloxide betaines (BI+-ArO-) and stoichiometric hydride reducing reagents was developed for carrying out desulfonylation reactions of N-sulfonyl-indoles,-amides, and-amines, and α-sulfonyl ketones. Measurements of absorption spectra and cyclic voltammograms as well as density functional theory (DFT) calculations were carried out to gain mechanistic information. In the catalytic system, visible-light-activated benzimidazoline aryloxides (BIH-ArO-), generated in situ by hydride reduction of the corresponding betaines BI+-ArO-, donate both an electron and a hydrogen atom to the substrates. A modified protocol was also developed so that a catalytic quantity of more easily prepared hydroxyaryl benzimidazolines (BIH-ArOH) is used along with a stoichiometric hydride donor to promote the photochemical desulfonylation reactions.
- Hasegawa, Eietsu,Tanaka, Tsukasa,Izumiya, Norihiro,Kiuchi, Takehiro,Ooe, Yuuki,Iwamoto, Hajime,Takizawa, Shin-Ya,Murata, Shigeru
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p. 4344 - 4353
(2020/04/09)
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- A NaH-promoted N-detosylation reaction of diverse p-toluenesulfonamides
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A NaH-mediated detosylation reaction of various Ts-protected indoles, azaheterocycles, anilines and dibenzylamine was reported. The method features cheap reagent, convenient operations, mild reaction conditions and broad substrate scope. Moreover, this study revealed that the loading of NaH in tosylation reactions of nitrogen-containing compounds with NaH as a base in DMA or DMF should be controlled due to the possibility of adverse detosylation.
- Sun, Wanwan,Chen, Xiaobei,Hu, Ying,Geng, Huihui,Jiang, Yuanrui,Zhou, Yuxin,Zhu, Wenjing,Hu, Min,Hu, Haohua,Wang, Xingyi,Wang, Xinli,Zhang, Shilei,Hu, Yanwei
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supporting information
(2020/10/05)
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- Electron Transfer Photoredox Catalysis: Development of a Photoactivated Reductive Desulfonylation of an Aza-Heteroaromatic Ring
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Herein, we report a protocol for desulfonylation of aza-heteroaromatic rings via photoinduced electron transfer and hydrogen atom transfer. This general protocol has a wide substrate range and moderate to good yields. The utility of the method was demonstrated by the chemoselective desulfonylation of a molecule containing both an aliphatic and an aromatic sulfonamide. (Figure presented.).
- Qiang-Liu,Liu, Yu-Xiu,Song, Hong-Jian,Wang, Qing-Min
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supporting information
p. 3110 - 3115
(2020/07/04)
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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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- Ni/Pd-catalyzed Suzuki-Miyaura cross-coupling of alcohols and aldehydes and C-N cross-coupling of nitro and amines: via domino redox reactions: base-free, hydride acceptor-free
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Domino oxidation-Suzuki-Miyaura cross-coupling of benzyl alcohols with phenylboronic acid and domino reduction-C-N cross-coupling of the nitro compounds with aryl halides were carried out using a strong Ni/Pd bimetallic redox catalyst. The catalyst bearing a copolymer with two Ni/Pd coordinated metals in porphyrin (derived from demetalated chlorophyll b) and salen-type ligands, and pyridine moiety as a base functionality all immobilized on magnetite NPs was synthesised and characterized. The domino oxidation cross-coupling reaction was accomplished under molecular O2 in the absence of any hydride acceptor or/and base. Also, the domino reduction C-N cross-coupling reaction was performed in the presence of NaBH4 without the need for any base and co-reductant. This multifunctional catalyst gave moderate to good yields for both coupling reactions with high chemoselectivity. A wide investigation was conducted to determine its mechanism and chemoselectivity.
- Ahmed, Rebin Omer,Kazemnejadi, Milad,Mahmoudi, Boshra
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p. 43962 - 43974
(2020/12/25)
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- Visible Light-Mediated (Hetero)aryl Amination Using Ni(II) Salts and Photoredox Catalysis in Flow: A Synthesis of Tetracaine
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We report a visible light-mediated flow process for C-N cross-coupling of (hetero)aryl halides with a variety of amine coupling partners through the use of a photoredox/nickel dual catalyst system. Compared to the method in batch, this flow process enables a broader substrate scope, including less-activated (hetero)aryl bromides and electron-deficient (hetero)aryl chlorides, and significantly reduced reaction times (10 to 100 min). Furthermore, scale up of the reaction, demonstrated through the synthesis of tetracaine, is easily achieved, delivering the C-N cross-coupled products in consistently high yield of 84% on up to a 10 mmol scale.
- Park, Boyoung Y.,Pirnot, Michael T.,Buchwald, Stephen L.
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p. 3234 - 3244
(2020/02/04)
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- Design, preparation and characterization of aerogel NiO-CuO-CoO/SiO2 nanocomposite as a reusable catalyst for C-N cross-coupling reaction
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Aerogels are porous, non-crystalline solid materials with high specific surface space, plentiful three-dimensional (3D) porous construction, ultra-low density and significant porosity. The aerogel nanocomposite is produced using sol-gel and supercritical drying processes. CO2 supercritical drying (SCD) is the most powerful process, ensuring optimal product properties such as high porosity, low density, and high thermal conductivity. On this account, we used the CO2 supercritical drying method to produce NiO-CuO-CoO/SiO2 nanocomposite aerogels and applied it as a reusable catalyst for the C-N cross-coupling reaction (Buchwald-Hartwig amination). Powerful catalytic activity for the C-N cross-coupling reaction was obtained for the new nanocomposite aerogel, that is, NiO-CuO-CoO/SiO2. The catalyst was characterized by X-ray Powder Diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), elemental mapping and Brunauer-Emmett-Teller (BET). Also, organic compounds were identified by melting point, Fourier-transform infrared spectroscopy (FT-IR) and hydrogen-1 nuclear magnetic resonance (1H NMR) analyses.
- Ghasemi, Amir Hossein,Naeimi, Hossein
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supporting information
p. 5056 - 5063
(2020/04/09)
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- Copper(I)–creatine complex on magnetic nanoparticles as a green catalyst for N- and O-arylation in deep eutectic solvent
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Immobilization of copper(I) ions on magnetic nanoparticles was performed using surface modification of Fe3O4 with creatine. Fe3O4?creatine-Cu(I) magnetic catalyst was synthesized and applied in C&bond;X cross-coupling reactions with aryl halides in a deep eutectic as a green solvent. The results indicate the Fe3O4?creatine-Cu(I) magnetic nanoparticles showed excellent activity and high stability. In addition, it was revealed that this catalyst can be recycled five times without significant loss in catalytic activity.
- Bagheri, Sepideh,Heydari, Akbar,Pazoki, Farzane,Radfar, Iman
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- COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF
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Provided in the present invention are a novel compound which can increase light emitting efficiency, stability and lifetime of an element, and an organic electronic element using the same, and an electronic device of the same. The present invention has a purpose of providing a compound which has high light emitting efficiency, low driving voltage, high heat resistance, improved color purity and lifetime of an element, an organic electronic element using the same, and an electronic device of the same. In an aspect, provided in the present invention is a compound represented by the following chemical formula.
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Paragraph 0161; 0166-0169
(2020/06/30)
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- Compound using dibenzo cycloheptene as core and application thereof
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The invention discloses compounds with 5H-dibenzo[a,d]cycloheptene as cores and an application of the compounds to OLED (organic light-emitting diode) devices. The compounds with 5H-dibenzo[a,d]cycloheptene as the cores are characterized in that central position of a heptyl ring of each compound is linked with a nitrogen-containing branch chain through phenyl, biphenyl or naphthyl. The compounds are not prone to crystallization and have good film forming property and heat stability as well as proper HOMO and LUMO energy level, by means of structure optimization of the devices, photoelectric property of the OLED devices can be improved effectively, and the service life of the OLED devices can be prolonged effectively.
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Paragraph 0050-0058
(2020/11/11)
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