100-01-6

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• Development of chemoselective photoreduction of nitro compounds under solar light and blue LED irradiation
• Solar light and blue light irradiation of the commercially available heterogeneous nano photocatalyst TiO2-P25 leads to reduction of nitro compounds to give the corresponding amines. The methodology provides a green and mild approach to this useful class of organic compounds. Aromatic nitro compounds containing a wide range of functional groups tolerated the conditions to give, chemoselectively the corresponding amines in excellent yields.
• Zand, Zahra,Kazemi, Foad,Hosseini, Saber

• p. 338 - 341

  (2014)
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• Gold catalysts supported on TiO2-nanotubes for the selective hydrogenation of p-substituted nitrobenzenes
• Gold nanoparticles supported on titania nanotubes (TiO2NT) were synthesized and employed as an efficient catalysts for the selective hydrogenation of nitrobenzenes. Materials characterization by N2 adsorption-desorption isotherms, XR
• Torres, Cecilia C.,Jiménez, Verónica A.,Campos, Cristian H.,Alderete, Joel B.,Dinamarca, Robinson,Bustamente, Tatiana M.,Pawelec, Barbara

• p. 21 - 27

  (2018)
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• A new palladium complex supported on magnetic nanoparticles and applied as an catalyst in amination of aryl halides, Heck and Suzuki reactions
• A simple, efficient and less expensive protocol for the phosphine-free C–C coupling reactions and synthesis of anilines in the presence of 2-aminobenzamide complex of palladium supported on Fe3O4 magnetic nanoparticles (Pd(0)-ABA-Fe3O4) has been reported. The Suzuki reaction was carried out in water or PEG using phenylboronic acid (PhB(OH)2) or sodium tetraphenyl borate (NaBPh4). Pd(0)-ABA-Fe3O4 has been found promising for Heck reaction of butyl acrylate, styrene or acrylonitrile with aryl halides (including Cl, Br and I). Also, Pd(0)-ABA-Fe3O4 has been found as efficient catalyst for the amination of aryl halides using aqueous ammonia. The products have been obtained in short reaction times and high yields. The catalyst was easily separated using an external magnet from the reaction mixture and reused for several runs without significant loss of its catalytic efficiency or palladium leaching. The leaching of catalyst has been examined by hot filtration and ICP-OES technique. The nanomagnetical catalyst was characterized by FTIR, TGA, XRD, VSM, TEM, SEM, EDS, DLS and ICP-OES techniques.
• Ghorbani-Choghamarani, Arash,Tahmasbi, Bahman,Noori, Nourolah,Ghafouri-nejad, Raziyeh

• p. 681 - 693

  (2017)
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• Purification of an aminopeptidase preferentially releasing N-terminal alanine from cucumber leaves and its identification as a plant aminopeptidase N
• In this study, a highly active foliar aminopeptidase preferentially releasing N-terminal alanine from artificial substrates was purified and characterized from cucumber (Cucumis sativus L. suyo). The enzyme had a molecular mass of 200 kDa consisting of two subunits of 95 kDa. It was a metalloprotease the pH optimum of which was 8 to 9. It cleaved Ala-, Gly-, Met-, Ser-, Leu-, Lys-, and Arg artificial substrates. An internal amino acid sequence was similar to those of aminopeptidase N (clan MA, family M1) of microorganisms, and was very similar to that of a putative aminopeptidase N of Arabidopsis thaliana. From these results, the highly active aminopeptidase in cucumber leaves was identified to be a plant aminopepitdase N.
• Yamauchi, Yasuo,Ejiri, Yukinori,Tanaka, Kiyoshi

• p. 2802 - 2805

  (2001)
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• 1,1,1-trimethylhydrazinium iodide: A novel, highly reactive reagent for aromatic amination via vicarious nucleophilic substitution of hydrogen
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• Pagoria, Philip F.,Mitchell, Alexander R.,Schmidt, Robert D.

• p. 2934 - 2935

  (1996)
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• Self-protonation upon the electroreduction of 2- and 4-nitrophenylhydroxylamines in aprotic media
• Cyclic voltammetry and controlled potential electrolysis were used to show that radical anions of 2- and 4-nitrophenylhydroxylamines electrochemically generated in a 0.1 M Bu4NClO4 solution in DMF undergo protonation with the startin
• Syroeshkin, Mikhail A.,Mendkovich, Andrei S.,Mikhalchenko, Ludmila V.,Rusakov, Alexander I.,Gul'tyai, Vadim P.

• p. 258 - 259

  (2009)
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• Structural characterization and function determination of a nonspecific carboxylate esterase from the amidohydrolase superfamily with a promiscuous ability to hydrolyze methylphosphonate esters
• The uncharacterized protein Rsp3690 from Rhodobacter sphaeroides is a member of the amidohydrolase superfamily of enzymes. In this investigation the gene for Rsp3690 was expressed in Escherichia coli and purified to homogeneity, and the three-dimensional structure was determined to a resolution of 1.8 ? The protein folds as a distorted (β/α)8-barrel, and the subunits associate as a homotetramer. The active site is localized to the C-terminal end of the β-barrel and is highlighted by the formation of a binuclear metal center with two manganese ions that are bridged by Glu-175 and hydroxide. The remaining ligands to the metal center include His-32, His-34, His-207, His-236, and Asp-302. Rsp3690 was shown to catalyze the hydrolysis of a wide variety of carboxylate esters, in addition to organophosphate and organophosphonate esters. The best carboxylate ester substrates identified for Rsp3690 included 2-naphthyl acetate (kcat/Km = 1.0 × 105 M-1 s-1), 2-naphthyl propionate (k cat/Km = 1.5 × 105 M-1 s -1), 1-naphthyl acetate (kcat/Km = 7.5 × 103 M-1 s-1), 4-methylumbelliferyl acetate (kcat/Km = 2.7 × 103 M-1 s-1), 4-nitrophenyl acetate (kcat/Km = 2.3 × 105 M-1 s-1), and 4-nitrophenyl butyrate (kcat/Km = 8.8 × 105 M -1 s-1). The best organophosphonate ester substrates included ethyl 4-nitrophenyl methylphosphonate (kcat/Km = 3.8 × 105 M-1 s-1) and isobutyl 4-nitrophenyl methylphosphonate (kcat/Km = 1.1 × 104 M-1 s-1). The (SP)-enantiomer of isobutyl 4-nitrophenyl methylphosphonate was hydrolyzed 10 times faster than the less toxic (RP)-enantiomer. The high inherent catalytic activity of Rsp3690 for the hydrolysis of the toxic enantiomer of methylphosphonate esters make this enzyme an attractive target for directed evolution investigations.
• Xiang, Dao Feng,Kumaran, Desigan,Swaminathan, Subramanyam,Raushel, Frank M.

• p. 3476 - 3485

  (2014)
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• Selective reduction of aromatic azides in solution/solid-phase and resin cleavage by employing BF3·OEt2/EtSH. Preparation of DC-81
• An efficient method for the reduction of aromatic azides in both solution and solid-phase has been developed by employing BF3·OEt2/EtSH. This report also describes resin cleavage employing this reagent system. Further, this protocol has been utilized for the solution as well as the solid-phase synthesis of pyrrolo[2,1-c][1,4]benzodiazepines, including the naturally occurring antibiotic DC-81 and fused [2,1-b]quinazolinones.
• Kamal, Ahmed,Shankaraiah,Reddy, K. Laxma,Devaiah

• p. 4253 - 4257

  (2006)
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• Nickel catalysis for hydrogenation of p-dinitrobenzene to p-phenylenediamine
• The activity of supported nickel catalysts (5–20% Ni) in the hydrogenation of p-dinitrobenzene to p-phenylenediamine was investigated. The catalysts were obtained by ureainduced precipitation. Activated carbon, alumina, titania, and silica gel were evaluated as supports. The most active catalysts, 5%Ni/TiO2 and 20%Ni/SiO2, provided 50–54% yields of p-phenylenediamine at complete dinitrobenzene conversion.
• Shuvalova,Kirichenko,Kustov

• p. 34 - 38

  (2017)
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• β-Sultams - A novel class of serine protease inhibitors
• N-Benzoyl β-sultam is an irreversible inactivator of elastase by sulfonation of the active site serine.
• Beardsell,Hinchliffe,Wood,Wilmouth,Schofield,Page

• p. 497 - 498

  (2001)
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• Photochemistry of p-Nitrophenyl Azide: Single-Electron-Transfer Reaction of the Triplet Nitrene
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• Liang, Tsuei-Yun,Schuster, Gary B.

• p. 546 - 548

  (1986)
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• Purification and characterization of an N-terminal acidic amino acid-specific aminopeptidase from soybean cotyledons (glycine max)
• A novel enzyme that catalyzes the efficient hydrolysis of Glu-Glu was isolated from soybean cotyledons by ammonium sulfate fractionation and successive column chromatographies of Q-sepharose, Phenyl sepharose, and Superdex 200. The apparent molecular mass of this enzyme was found to be 56kDa and 510 kDa by SDS-polyacrylamide gel electrophoresis and Superdex 200 HR 10/30 column chromatography respectively. The enzyme had high activity against Glu-/7-nitroanilide (/NA) and Asp-pNA, whereas Leu-pNA, Phe-pNA, Ala-/;NA, and Pro-pNA were not hydrolyzed. The synthetic dipeptides Glu-Xxx and Asp-Xxx were hydrolyzed, but Xxx-Glu was not. The digestion of a Glu-rich oligopep-tide, chromogranin A (Glu-Glu-Glu-Glu-Glu-Met-Ala-Val-Val-Pro-Gln-Gly- Leu-Phe-Arg-Gly-NH2) using this purified enzyme was also investigated. Glutamic acid residues were cleaved one by one from the N-terminus. These observations indicate that the enzyme removes glutamyl or aspartyl residues from N-terminal acidic amino acid-containing peptides. It is thought that it was an N-terminal acidic amino acid-specific aminopeptidase from a plant.
• Asano, Minao,Nakamura, Nami,Kawai, Misako,Miwa, Tetsuya,Nio, Noriki

• p. 113 - 118

  (2010)
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• One-pot aromatic amination based on carbon-nitrogen coupling reaction between aryl halides and azido compounds
• An efficient copper-mediated C-N coupling reaction between various aryl halides and azido compounds to produce the corresponding aromatic primary amines was established. The present amination is apparently involved in both the reduction of an azido functionality to the corresponding primary amino group and its cross-coupling reaction with aryl halides in a one-pot manner. The present amination could be applied to the synthesis of procaine, a local anesthetic drug. A mechanistic study indicated that 2-aminoethanol could work as a major hydrogen donor and the reaction would proceed without the formation of the intermediary aryl azide.
• Maejima, Toshihide,Shimoda, Yutaka,Nozaki, Kei,Mori, Shigeki,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao

• p. 1712 - 1722

  (2012)
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• Reduction of organic azides to amines using reusable Fe3O 4 nanoparticles in aqueous medium
• Aromatic, heteroaromatic and sulfonyl azides were conveniently reduced to the corresponding amines in excellent yields using hydrazine hydrate in the presence of iron oxide nanoparticles. The Fe3O4-MNPs could be easily separated by an external magnet, and recycled ten times without significant loss of the catalytic efficiency. The Royal Society of Chemistry 2013.
• Pagoti, Sreenivasarao,Surana, Subham,Chauhan, Ajay,Parasar, Bibudha,Dash, Jyotirmayee

• p. 584 - 588

  (2013)
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• Selective nitrolytic deprotection of N-BOC-amines and N-BOC-amino acids derivatives
• The extension of the deprotection procedure using HNO3 in CH2Cl2 to a number of appropriately selected N-BOC-masked amines and derivatives of natural amino acids was investigated. The method was found to work effectively with almost all tested substrates, with the exception of activated aromatic amines and heterocycles which underwent unavoidable faster oxidation. Alanine, phenylalanine, serine and lysine derivatives were efficiently deprotected, as well as dipeptide Ala-Phe, preserving the configuration of the substrates and without affecting copresent Z and ester functions, with a remarkable selectivity towards acid sensitive t-butyl esters. The obtained amino acids esters, isolated and characterized in the form of nitrates salts, proved to be suitable intermediates to be used in peptide synthesis.
• Strazzolini, Paolo,Melloni, Tiziana,Giumanini, Angelo G

• p. 9033 - 9043

  (2001)
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• Mo(CO)6 Mediated Selective Reduction of Azides and Nitro Compounds to Amines under Neutral Conditions
• Mo(CO)6 selectively reduces various azides and nitro compounds to the corresponding amines in refluxing ethanol.
• Iyer, Suresh,Kulkarni, Girish M.

• p. 721 - 725

  (2004)
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• Selective Reduction of Nitroarenes to Arylamines by the Cooperative Action of Methylhydrazine and a Tris(N-heterocyclic thioamidate) Cobalt(III) Complex
• We report an efficient catalytic protocol that chemoselectively reduces nitroarenes to arylamines, by using methylhydrazine as a reducing agent in combination with the easily synthesized and robust catalyst tris(N-heterocyclic thioamidate) Co(III) complex [Co(κS,N-tfmp2S)3], tfmp2S = 4-(trifluoromethyl)-pyrimidine-2-thiolate. A series of arylamines and heterocyclic amines were formed in excellent yields and chemoselectivity. High conversion yields of nitroarenes into the corresponding amines were observed by using polar protic solvents, such as MeOH and iPrOH. Among several hydrogen donors that were examined, methylhydrazine demonstrated the best performance. Preliminary mechanistic investigations, supported by UV-vis and NMR spectroscopy, cyclic voltammetry, and high-resolution mass spectrometry, suggest a cooperative action of methylhydrazine and [Co(κS,N-tfmp2S)3] via a coordination activation pathway that leads to the formation of a reduced cobalt species, responsible for the catalytic transformation. In general, the corresponding N-arylhydroxylamines were identified as the sole intermediates. Nevertheless, the corresponding nitrosoarenes can also be formed as intermediates, which, however, are rapidly transformed into the desired arylamines in the presence of methylhydrazine through a noncatalytic path. On the basis of the observed high chemoselectivity and yields, and the fast and clean reaction processes, the present catalytic system [Co(κS,N-tfmp2S)3]/MeNHNH2 shows promise for the efficient synthesis of aromatic amines that could find various industrial applications.
• Ioannou, Dimitris I.,Gioftsidou, Dimitra K.,Tsina, Vasiliki E.,Kallitsakis, Michael G.,Hatzidimitriou, Antonios G.,Terzidis, Michael A.,Angaridis, Panagiotis A.,Lykakis, Ioannis N.

• p. 2895 - 2906

  (2021)
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• Chemoselective N-deacetylation under mild conditions
• A mild and efficient chemoselective N-deacetylation using the Schwartz reagent at room temperature in rapid time is described. The mild and neutral conditions enable orthogonal N-deacetylation in the presence of some of the common protecting groups (viz. Boc, Fmoc, Cbz, Ts). The deprotection conditions did not induce any epimerization at the chiral amino centre.
• Sultane, Prakash R.,Mete, Trimbak B.,Bhat, Ramakrishna G.

• p. 261 - 264

  (2014)
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• Electrochemical control of the catalytic activity of immobilized enzymes
• Regulation of the catalytic activity of enzymes immobilized on carbon nanotube electrodes was achieved by changing their local pH environment using electrochemical reactions. Reduction of oxygen increased the interfacial pH while oxidation of ascorbate decreased it, thus allowing changing rates of enzymatic reactions of electrode-immobilized amyloglucosidase and trypsin enzymes over a wide activity range.
• Kadambar, Vasantha Krishna,Bellare, Madhura,Bollella, Paolo,Katz, Evgeny,Melman, Artem

• p. 13800 - 13803

  (2020)
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• Copper-catalyzed coupling of aryl halides and nitrite salts: A mild Ullmann-type synthesis of aromatic nitro compounds
• Nitration of aromatic halides proceeded smoothly in the presence of catalytic amounts of Cu bronze and N,N′-dimethylethylenediamine. Sodium nitrite-18-crown-6, or tetra-n-butylammonium nitrite (n-Bu4NNO 2) turned out to be efficient nitrating agents. The aromatic nitro compounds were synthesized under essentially neutral conditions.
• Saito, Shinichi,Koizumi, Yuichiro

• p. 4715 - 4717

  (2005)
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• Hydrogen-bond-regulated distinct functional-group display at the inner and outer wall of vesicles
• A unique supramolecular strategy enables the unidirectional assembly of two bola-shaped unsymmetric π-amphiphiles, NDI-1 and NDI-2, which feature a naphthalene-diimide chromophore connected to nonionic and anionic head groups on opposite arms. The amphiphiles differ only in the location of a hydrazide group, which is placed either on the nonionic or on the anionic arm of NDI-1 and NDI-2, respectively. The formation of hydrogen bonds between the hydrazides, which compensates for electrostatic and steric factors, promotes unidirectional alignment and the formation of monolayer vesicles. The zeta potentials and cation-assisted quantitative precipitation reveal negatively charged and nonionic outer surfaces for NDI-1 and NDI-2, respectively, indicating that hydrogen bonding also dictates the directionality of the monolayer curvature, ensuring that in both cases, the hydrazides remain at the inner wall to benefit from stronger hydrogen bonding where they are in closer proximity. This is reflected in their different abilities to inhibit α-chymotrypsin, which possesses a positively charged surface: NDI-1 induced an inhibition of 80% whereas hardly any inhibition was observed with NDI-2.
• Sikder, Amrita,Das, Anindita,Ghosh, Suhrit

• p. 6755 - 6760

  (2015)
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• Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst
• Small zero-valent copper nanoparticles (CuNPs) have been straightforwardly prepared from Cu(I) and Cu(II) precursors in glycerol and in the presence of polyvinylpyrrolidone as stabilizer. Thanks to the negligible vapor pressure of the solvent, these original nano-systems could be directly characterized in glycerol as well as in the solid state, exhibiting relevantly homogeneous colloidal dispersions, also even after catalysis. CuNPs coming from the well-defined coordination complex di-μ-hydroxobis[(N,N,N′,N′-tetramethylethylenediamine)copper(II)] chloride {[Cu(κ2-N,N-TMEDA)(μ-OH)]2Cl2} have been highly efficient in C–C and C–heteroatom bond formation processes. This new catalytic system has proved its performance in C–N couplings and in the synthesis of differently substituted propargylic amines through cross-dehydrogenative couplings, multi-component reactions such as A3 (aldehyde-alkyne-amine) and KA2 (ketone-alkyne-amine) couplings, as well as in the formation of heterocycles such as benzofurans, indolizines, and quinolines under smooth conditions. No significant copper amount was detected in the extracted organic compounds from the catalytic phase by inductively coupled plasma-atomic emission spectroscopic (ICP-AES) analyses, proving a highly efficient immobilization of copper nanoparticles in glycerol. From a mechanistic point of view, spectroscopic data (infrared and ultraviolet-visible spectra) agree with a surface-like catalytic reactivity. (Figure presented.).
• Dang-Bao, Trung,Pradel, Christian,Favier, Isabelle,Gómez, Montserrat

• p. 2832 - 2846

  (2017)
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• Development and Application of Efficient Ag-based Hydrogenation Catalysts Prepared from Rice Husk Waste
• The development of strategies for the sustainable management and valorization of agricultural waste is of outmost importance. With this in mind, we report the use of rice husk (RH) as feedstock for the preparation of heterogeneous catalysts for hydrogenation reactions. The catalysts were prepared by impregnating the milled RH with a silver nitrate solution followed by carbothermal reduction. The composition and morphology of the prepared catalysts were fully assessed by IR, AAS, ICP-MS, XPS, XRD and STEM techniques. This novel bio-genic silver-based catalysts showed excellent activity and remarkable selectivity in the hydrogenation of nitro groups in both aromatic and aliphatic substrates, even in the presence of reactive functionalities like halogens, carbonyls, borate esters or nitriles. Recycling experiments showed that the catalysts can be easily recovered and reused multiple times without significant drop in performance and without requiring re-activation.
• Unglaube, Felix,Kreyenschulte, Carsten Robert,Mejía, Esteban

• p. 2583 - 2591

  (2021)
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• Chemoselective reduction of azides with sodium sulfide hydrate under solvent free conditions
• Sodium sulfide hydrate has been employed for an efficient reduction of a variety of azides to the primary amines in good-to-excellent yields under solvent-free system and without perturbing many active functionalities such as ether, carbonyl, sulfonyl, and nitro.
• Kazemi, Foad,Kiasat, Ali Reza,Sayyahi, Sohyl

• p. 1813 - 1817

  (2004)
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• Highly efficient nitrobenzene and alkyl/aryl azide reduction in stainless steel jars without catalyst addition
• The mechanochemical and selective reduction of aryl nitro and aryl/alkyl azide derivatives, with either formate salts or hydrazine, to the corresponding, synthetically useful amines occurs in excellent yields in a planetary ball mill without the addition of a catalyst. This newly developed and solvent-free protocol is efficient, fast and does not require the addition of a metal hydrogenation catalyst as the stainless steel jar itself fulfils that role. The method has been applied to a broad range of compounds and excellent yields have been obtained. The formylation of alkyl amines has been successfully performed, by means of mechanochemical activation, in the presence of ammonium formate alone.
• Martina, Katia,Baricco, Francesca,Tagliapietra, Silvia,Moran, Maria Jesus,Cravotto, Giancarlo,Cintas, Pedro

• p. 18881 - 18888

  (2018)
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• A mild procedure for the clay catalyzed selective removal of the tert- butoxycarbonyl protecting group from aromatic amines
• The application of solid acidic catalysts for the selective removal of N-Boc protection is presented in this report. Montmorillonite K10 was found to be an effective catalyst in removing aromatic N-Boc groups while leaving aliphatic N-Boc amines untouched.
• Shaikh, Nadim S.,Gajare, Anil S.,Deshpande, Vishnu H.,Bedekar, Ashutosh V.

• p. 385 - 387

  (2000)
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• 100% selective yield of m-nitroaniline by rutile TiO2 and m-phenylenediamine by P25-TiO2 during m-dinitrobenzene photoreduction
• Photoreduction of m-dinitrobenzene (25 μmol) in the deaerated aqueous iso-propanol exhibits 100% selective yield of m-nitroaniline (25 μmol) by rutile TiO2 (50 mg) or m-phenylenediamine (25 μmol) by P25-TiO2 separately under 8 and 4 h of UV light irradiation (125 W Hg arc, 10.4 mW/cm2), respectively. It revealed that insertion of a second -NO2 in nitrobenzene ring has an important role in expediting -NO2 reduction to -NH2 as compared to a negligible reduction of nitrobenzene under similar conditions, indicating that electron withdrawing groups lower the electron density on -NO2 present on meta position and favor quick reduction of the -NO2 group.
• Kaur, Jaspreet,Pal, Bonamali

• p. 25 - 28

  (2014)
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• Palladium-catalyzed cleavage of O/N-propargyl protecting groups in aqueous media under a copper-free condition
• (Figure presented) A copper-free palladium-mediated cleavage of O/N-propargyl bonds in aqueous media has been investigated, affording a mild and convenient method for the deprotection of phenols and anilines. The methodology could be utilized for the selective removal of propargyl groups from aryl ethers and amines without affecting a variety of unprotected functional groups present in the substrates. The mechanism and scope of the reaction is discussed.
• Pal, Manojit,Parasuraman, Karuppasamy,Yeleswarapu, Koteswar Rao

• p. 349 - 352

  (2003)
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• A Highly Water-Dispersible/Magnetically Separable Palladium Catalyst: Selective Transfer Hydrogenation or Direct Reductive N-Formylation of Nitroarenes in Water
• Simple ion exchange of the chloride anion of an ionic-liquid-functionalized magnetic nanoparticle with [PdCl4]2- provided a highly water-dispersible and magnetically separable palladium catalyst that exhibited excellent activity toward transfer hydrogenation reactions in water as a solvent. The catalyst demonstrated outstanding performance in aqueous-phase transfer hydrogenation of various nitroarenes in a highly chemo- and regioselective manner by using HCOONH4 as a low-cost, green, and easily available hydrogen donor. Also, by using only 0.25 mol % of the catalyst and formic acid as both a hydrogen donor and formylating agent, the catalyst showed excellent activity in the one-pot, direct synthesis of N-arylformamides from nitroarenes in water as a solvent. Notably, owing to the presence of a hydrophilic ionic liquid on the surface of silica-coated iron oxide nanoparticles, the catalyst showed highly stable dispersion in water, as evidenced by the zeta potential and extremely low affinity to the organic phase. These features make this catalyst system suitable for an efficient double-separation strategy (successive extraction/final magnetic separation). The recovered aqueous phase containing the catalyst can be simply and efficiently reused in eight runs without a decrease in activity and can be easily separated from the aqueous phase at the end of the process by applying an external magnetic field.
• Karimi, Babak,Mansouri, Fariborz,Vali, Hojatollah

• p. 1750 - 1759

  (2015)
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• Cobalt Entrapped in N,S-Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid
• Catalysts with Co nanoparticles (NPs) entrapped in N,S-codoped carbon shells were successfully fabricated by pyrolysis of porous organic polymers (POPs) with cobalt salts. The encapsulated structure consisting of Co NPs and N,S-codoped carbon layers was verified by TEM, XRD, and X-ray photoelectron spectroscopy. The catalysts displayed excellent activity and stability for the catalytic transfer hydrogenation (CTH) of nitrobenzene with formic acid under base-free conditions. Furthermore, the resultant catalysts allowed for highly efficient and selective transfer hydrogenation of various functionalized nitroarenes to the corresponding anilines. Through control experiments, the covered Co NPs were identified as active sites for CTH. The incorporation of S into the N-doped carbon lattice promoted the electron transfer from metallic cobalt NPs to their shells, which played a significant role in the acceleration of CTH. Moreover, the Co-NSPC-850 catalyst pyrolyzed at 850 °C showed excellent stability in the recycling experiments.
• Guo, Haotian,Gao, Ruixiao,Sun, Mingming,Guo, Hao,Wang, Bowei,Chen, Ligong

• p. 487 - 494

  (2019)
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• Revisiting ring-degenerate rearrangements of 1-substituted-4-imino-1,2,3-triazoles
• The 1-substituted-4-imino-1,2,3-triazole motif is an established component of coordination compounds and bioactive molecules, but depending on the substituent identity, it can be inherently unstable due to Dimroth rearrangements. This study examined parameters governing the ring-degenerate rearrangement reactions of 1-substituted-4-imino-1,2,3-triazoles, expanding on trends first observed by L’abbé et al. The efficiency of condensation between 4-formyltriazole and amine reactants as well as the propensity of imine products towards rearrangement was each strongly influenced by the substituent identity. It was observed that unsymmetrical condensation reactions conducted at 70 °C produced up to four imine products via a dynamic equilibrium of condensation, rearrangement and hydrolysis steps. Kinetic studies utilizing 1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbaldehyde with varying amines showed rearrangement rates sensitive to both steric and electronic factors. Such measurements were facilitated by a high throughput colorimetric assay to directly monitor the generation of a 4-nitroaniline byproduct.
• Fletcher, James T.,Hanson, Matthew D.,Christensen, Joseph A.,Villa, Eric M.

• p. 2098 - 2105

  (2018)
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• Tingle,Rolker

• p. 1890

  (1908)
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• Secretory leukocyte protease inhibitor: Inhibition of human immunodeficiency virus-1 infection of monocytic THP-1 cells by a newly cloned protein
• The ability of the salivary protein, secretory leukocyte protease inhibitor (SLPI), to inhibit human immunodeficiency virus-1 (HIV-1) infection in vitro has been reported previously and has led to the suggestion that SLPI may be partially responsible for
• Shine,Wang,Konopka,Burks,Duzgunes,Whitman

• p. 249 - 263

  (2002)
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• Development of molecular sieves-supported palladium catalyst and chemoselective hydrogenation of unsaturated bonds in the presence of nitro groups
• The chemoselective hydrogenation of unsaturated bonds and azide functionalities is achieved in the presence of nitro groups by a heterogeneous palladium catalyst supported on molecular sieves (MS3A). The present method shows a widerange of applicability with regard to substrates and the catalyst can be easily prepared and reused at least three times without any loss of activity.
• Maegawa, Tomohiro,Takahashi, Tohru,Yoshimura, Masatoshi,Suzuka, Hiroyasu,Monguchi, Yasunari,Sajiki, Hironao

• p. 2091 - 2095

  (2009)
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• A novel trypsin Kazal-type inhibitor from Aedes aegypti with thrombin coagulant inhibitory activity
• Kazal-type inhibitors play several important roles in invertebrates, such as anticoagulant, vasodilator and antimicrobial activities. Putative Kazal-type inhibitors were described in several insect transcriptomes. In this paper we characterized for the fi
• Watanabe, Renata M.O.,Soares, Tatiane S.,Morais-Zani, Karen,Tanaka-Azevedo, Anita M.,Maciel, Ceres,Capurro, Margareth L.,Torquato, Ricardo J.S.,Tanaka, Aparecida S.

• p. 933 - 939

  (2010)
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• N3 as an efficient reagent for the Schmidt reactions of ketones, arylaldehydes and aromatic carboxylic acids
• Schmidt reaction of arylaldehydes, ketones and aromatic carboxylic acids using task-specific ionic liquid, [bmim]N3 in the presence of AcOH/H2SO4 proceeds at 50-60 °C within 2-4 h to give the corresponding products. Benzaldehydes containing electron releasing groups afforded to the related benzamide derivatives. Benzonitrile derivatives were formed from the reaction of benzaldehydes containing electron withdrawing groups under these conditions. High yields of the related amides and anilines were obtained from the reaction of a variety of ketones and aromatic carboxylic acids, respectively, utilizing this procedure.
• Valizadeh, Hassan,Gholipour, Hamid,Ahmadi, Mina,Vaghefi, Sevil

• p. 1287 - 1294

  (2014)
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• Unprecedented iron-catalyzed selective hydrogenation of activated amides to amines and alcohols
• The first example of hydrogenation of amides homogeneously catalyzed by an earth-abundant metal complex is reported. The reaction is catalyzed by iron PNP pincer complexes. A wide range of secondary and tertiary N-substituted 2,2,2-trifluoroacetamides were hydrogenated to form amines and trifluoroethanol.
• Garg, Jai Anand,Chakraborty, Subrata,Ben-David, Yehoshoa,Milstein, David

• p. 5285 - 5288

  (2016)
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• Pre-steady-state kinetic studies of rat kidney γ-glutamyl transpeptidase confirm its ping-pong mechanism
• The enzyme γ-glutamyl transpeptidase (GGT) is implicated in cellular detoxification, the biosynthesis of leukotrienes and control of the physiological concentration of glutathione. It also plays important roles in Parkinson's disease, diabetes, apoptosis inhibition and cancer drug resistance. It catalyses the breakdown of its in vivo substrate, glutathione, by cleaving the amide bond between the γ-glutamyl and the cysteinylglycine moieties. Threonine is proposed to act as the nucleophile of GGT in the formation of the γ-glutamyl acyl enzyme intermediate during the acylation step. The γ-glutamyl moiety is then transferred to a primary amine acceptor substrate (an amino acid or dipeptide) or to a water molecule, to form a compound containing a new isopeptide bond or glutamate in the transamidation or hydrolysis reactions, respectively. In spite of the importance of the role of GGT in human physiology, there is a lack of information about the mechanisms of its catalytic reactions, and in particular the nature of the intermediate formed during the acylation step. In order to gain insight into the formation of the acyl enzyme intermediate, different D-γ-glutamylanilides substituted in the para position with electron-withdrawing and electron-, donating groups were used as donor substrates under conditions where water served as acceptor substrate. A Hammett plot with a slope of zero was obtained for the steady-state hydrolysis reaction for which deacylation is the rate-limiting step. To confirm the ping-pong mechanism, pre-steady-state kinetics of this reaction were then performed with the donor substrate D-γ-glutamyl-p-nitroanilide, which liberates the chromophore p-nitroaniline. Experiments using a stopped- flow spectrometer and a rapid mix-quench apparatus gave biphasic traces with a burst up to ～ 65 ms, the amplitude of which corresponds well with the concentration of the enzyme. These burst kinetics were also observed in the presence of L-methionine at concentrations ～ 15-fold below its KM value, where deacylation would still be rate limiting. These observations are consistent with the formation of an intermediate during the rapid acylation step and support the modified ping-pong mechanism proposed for GGT- mediated hydrolysis and aminolysis. Copyright
• Keillor, Jeffrey W.,Ménard, Annie,Castonguay, Roselyne,Lherbet, Christian,Rivard, Caroline

• p. 529 - 536

  (2004)
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• Synthesis and kinetics of disassembly for silyl-containing ethoxycarbonyls using fluoride ions
• In this study, a series of silyl-containing ethoxycarbonates and ethoxycarbamates on electron poor anilines and phenols were synthesized and their kinetics of disassembly determined in real-time upon exposure to fluoride ion sources at room temperature. The results provide a greater understanding of stability and kinetics for silyl-containing protecting groups that eliminate volatile molecules upon removal, which will allow for simplification of orthogonal protection in complex organic molecules.
• Camerino, Eugene,Daniels, Grant C.,Wynne, James H.,Iezzi, Erick B.

• p. 1884 - 1888

  (2018)
• Read Online

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• Scott,F.L.,Fenton,D.F.

• p. 685 - 688

  (1970)
• Read Online

• Methyltriphenylphosphonium tetrahydroborate (MePh3PBH4). A stable, selective and versatile reducing agent
• Methyltriphenylphosphonium tetrahydroborate as a stable quaternary phosphonium borohydride is introduced. This compound is able to reduce aldehydes, ketones, acyl chlorides, and azides efficiently in CH2Cl2. α,β-Unsaturated carbonyl compounds are reduced selectively via 1,2-reduction. The effect of Lewis acids upon the mode and the rate of the reaction of epoxides and acetophenone are also described. This reagent is also able to bring about reductions effectively in the absence of solvent.
• Firouzabadi, Habib,Adibi, Mina

• p. 125 - 147

  (1998)
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• An Efficient Method for the Hofmann Degradation of Amides by Use of Benzyltrimethylammonium Tribromide
• The reaction of amides with a calculated amount of benzyltrimethylammonium tribromide in aqueous sodium hydroxide under mild conditions gave corresponding amines in fairly good yields.
• Kajigaeshi, Shoji,Asano, Kohichi,Fujisaki, Shizuo,Kakinami, Takaaki,Okamoto, Tsuyoshi

• p. 463 - 464

  (1989)
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• Amidines. III. A kinetic study of acid hydrolysis of unsymmetrical N1,N2-disubstituted amidines
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• Ono,Todoriki,Araya,Tamura

• p. 1158 - 1164

  (1990)
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• Purification and properties of soluble and bound γ- glutamyltransferases from radish cotyledon
• Soluble and cell wall bound γ-glutamyltransferases (GGTs) were purified from radish (Raphanus sativus L.) cotyledons. Soluble GGTs (GGT I and II) had the same Mr of 63,000, and were composed of a heavy subunit (Mr, 42,000) and a light one (Mr, 21,000). The properties of GGT I and II were similar. Bound GGTs (GGT A and B) were purified to homogeneity from the pellet after the extraction of soluble GGTs. GGT A and B were monomeric proteins with an Mr of 61,000. The properties of GGT A and B were similar. Thus, bound GGTs were distinguished from soluble GGTs. The optimal pHs of soluble and bound GGTs were about 7.5. Both soluble and bound GGTs utilized glutathione, γ-L-glutamyl-p-nitroanilide, oxidized glutathione and the conjugate of glutathione with monobromobimane as substrates, and were inhibited by acivicin, but soluble GGTs were also distinguished from bound GGTs with regard to these properties.
• Nakano, Yoshihiro,Okawa, Satoshi,Yamauchi, Takayoshi,Koizumi, Yukio,Sekiya, Jiro

• p. 369 - 376

  (2006)
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• The Kinetics and Mechansim of the Hydrolysis of p-Nitrophenyl Isothiocyanate Promoted by Soft Metal Ions
• The hydrolysis of p-nitrophenyl isothiocyanate in aqueous acid solution is powerfully promoted by the Ag+ and Hg2+ ions.The organic product is p-nitroaniline.The mercury-promoted reaction is first order in isothiocyanate and in , and has ΔH(excit.) = 56 +/- 2kJ mol-1, ΔS(excit.) = -53 +/- 4 J K-1 mol-1, and kH2O/kD2O = 1.12 +/- 0.05 at 25.0 deg C.The behaviour with silver is similar: promotion is principally first order in , but in H2O there is evidence for a small kinetic term in 2. ΔH(excit.) = 59 +/- 2kJ mol-1 and ΔS(excit.) = -88 +/- 3 J K-1 mol-1 for the first-order reaction, and ΔH(excit.) = 25 +/- 5 kJ mol-1 and ΔS(excit.) = -202 +/- 12 j K-1 mol-1 for the route second order in .Use of D2O removes the second-order term, and kH2O/kD2O = 1.07 +/- 0.06 for the route involving one Ag+ ion pre-equilibrium, followed by a rate-determining attack of water to give the soft metal derivative of the corresponding thiocarbamic acid as a rapidly decomposition intermediate.
• Satchell, Derek P. N.,Satchell, Rosemary S.

• p. 303 - 306

  (1991)
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• THE MECHANISM OF THE INTERACTION OF N-ARYL-O-PIVALOYLHYDROXYLAMINES WITH REDUCING METAL IONS
• Evidence which supports a stepwise electron transfer process for the reduction of 1 by Fe(2+) and Cu(+) is presented.
• Lagerman, Robert K.,Novak. Michael

• p. 1923 - 1926

  (1989)
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• Facile and efficient amination of organic halides catalyzed by copper sulfate in PEG1000-DIL/methylcyclohexane temperature-dependent biphasic system
• A simple, efficient, and environmentally friendly procedure for the amination of organic halides catalyzed by CuSO4·5H 2O in PEG1000-DIL/methylcyclohexane temperature-dependent biphasic system is described. The product can be easily isolated by a simple decantation, and the catalytic system can be recycled and reused without loss of catalytic activity.
• Hu, Yu-Lin,Wanga, Peng-Cheng,Chen, Tian,Lu, Ming

• p. 604 - 611

  (2010)
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• APPLICATION OF MICROWAVE ENERGY TO ORGANIC SYBNTHESIS: IMPROVED TECHNOLOGY
• The application of microwave energy to the sulfonation of naphthalene and anthraquinone, to the amination of p-chloronitrobenzene, and to the hydrosilylation of 2- and 4-vinylpyridine has been studied.Though faster (5-360-fold) reactions were observed problems were encountered with the available microwave technology.These were overcome by using a microwave oven equipped with stirring facility and both temperature and pressure control.
• Abramovitch, R. A.,Abramovitch, D. A.,Iyanar, K.,Tamareselvy, K.

• p. 5251 - 5254

  (1991)
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• A palladium complex immobilized onto mesoporous silica: a highly efficient and reusable catalytic system for carbon–carbon bond formation and anilines synthesis
• A palladium complex supported on functionalized mesoporous silica MCM-41 proved to be a highly efficient, recoverable catalyst for C–C coupling reactions and amination of aryl halides to afford anilines. The nanocatalyst was characterized by FT-IR spectroscopy, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, N2 adsorption–desorption isotherms and inductively coupled plasma analysis. The catalyst could be reused for several consecutive runs without significant loss of activity. The excellent yields of products, simple reaction procedures and short reaction times are the main advantages of this methodology.
• Nikoorazm, Mohsen,Noori, Nourolah,Tahmasbi, Bahman,Faryadi, Sara

• p. 469 - 481

  (2017)
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• Continuous-Flow Electrophilic Amination of Arenes and Schmidt Reaction of Carboxylic Acids Utilizing the Superacidic Trimethylsilyl Azide/Triflic Acid Reagent System
• A continuous flow protocol for the direct stoichiometric electrophilic amination of aromatic hydrocarbons and the Schmidt reaction of aromatic carboxylic acids using the superacidic trimethylsilyl azide/triflic acid system is described. Optimization of reagent stoichiometry, solvent, reaction time, and temperature led to an intensified protocol at elevated temperatures that allows the direct amination of arenes to be completed within 3 min at 90 °C. In order to improve the selectivity and scope of this direct amination protocol, aromatic carboxylic acids were additionally chosen as substrates. Selected carboxylic acids could be converted to their corresponding amine counterparts in good to excellent yields (11 examples, 55-83%) via a Schmidt reaction employing similar flow reaction conditions (5 min at 90 °C) and a similar reactor setup as for the amination. The safety issues derived from the explosive, toxic, and volatile hydrazoic acid intermediate, the corrosive nature of triflic acid, and the exothermic quenching were addressed by designing a suitable continuous flow reaction setup for both types of transformations.
• Chen, Yuesu,Gutmann, Bernhard,Kappe, C. Oliver

• p. 9372 - 9380

  (2016)
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• Electroreductive synthesis of polyfunctionalized pyridin-2-ones from acetoacetanilides and carbon disulfide with oxygen evolution
• A chemical reductant or a sacrificial electron donor is required in any reduction reactions, generally resulting in undesired chemical waste. Herein, we report a reductant-free reductive [3 + 2 + 1] annulation of β-keto amides with CS2 enabled by the synergy of electro/copper/base using water as an innocuous anodic sacrifice with O2 as a sustainable by-product. This electrochemical protocol is mild and provides access to polyfunctionalized pyridin-2-ones from simple starting materials in a single step.
• Gao, Shulin,Hu, Xi,Li, Weili,Li, Yanni,Liang, Deqiang,Ma, Zhongxiao,Wang, Baoling,Xu, Lichun,Zhang, Xin
• supporting information

  p. 1013 - 1018

  (2022/02/16)
• 

• Magnetically‐recoverable Schiff base complex of Pd(II) immobilized on Fe3O4@SiO2 nanoparticles: an efficient catalyst for the reduction of aromatic nitro compounds to aniline derivatives
• Fe3O4@SiO2/Schiff base/Pd(II) is reported as a magnetically recoverable heterogeneous catalyst for the chemoselective reduction of aromatic nitro compounds to the corresponding amines through catalytic transfer hydrogenation (CTH). In this regard, a small amount of the nanocatalyst (0.52?mol% Pd) and hydrazine hydrate, showing safe characteristics and perfect ability as the hydrogen donor, were added to the nitro substrates. The experiments described the successful reduction of aromatic nitro compounds with good to excellent yields and short reaction times. The catalyst, due to its magnetic property, could be simply separated from the reaction mixture by a permanent magnet and reused in seven consecutive reactions without considerable loss in its activity. Moreover, the leaching of Pd was only 3.6% after the seventh run. Thus, the most striking feature of this method is to use a small amount of the magnetic nanocatalyst along with a cheap and safe hydrogen source to produce the important amine substances selectively, which makes the method economical, cheap, environmentally friendly, and simple. Graphic abstract: [Figure not available: see fulltext.]
• Azadi, Sedigheh,Esmaeilpour, Mohsen,Sardarian, Ali Reza

• p. 809 - 821

  (2021/07/20)
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• [1+1] Copper(II) macrocyclic Schiff base complex on rGO as a photocatalyst for reduction of nitroaromatics compounds under visible-light irradiation
• In this work, [1 + 1] macrocyclic Copper(II) Schiff base complex ([CuL](NO3)2.H2O) was synthesized and grafted on reduced graphene oxide successfully. The novel prepared sample was characterized by physico-chemical techniques and used as a photocatalyst for the reduction of nitroaromatic compounds to their amine derivatives at room temperature under visible-light irradiation with hydrazine mono hydrate. From the prepared samples, reduced graphene oxide loaded with 30% [CuL](NO3)2.H2O catalyst (rGO/CuM30) shows the best efficiency for converting different nitroaromatic compounds to the corresponding amino compounds using visible light. As-prepared catalyst illustrated excellent activity for the reduction of 2-nitrophenol to 2-aminophenol (100% conversion) in only 90 min. Finally, the catalyst could be recovered for five times and reused without decreasing of its efficiency.
• Ghalebin, Saeed Nasiri,Bezaatpour, Abolfazl,Sadr, Moayad Hossaini,Sadjadi, Mirabdullah Seyed,Moghaddam, Mohammad Khodadadi,Szunerits, Sabine

• (2021/01/26)
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• A mild and selective Cu(II) salts-catalyzed reduction of nitro, azo, azoxy, N-aryl hydroxylamine, nitroso, acid halide, ester, and azide compounds using hydrogen surrogacy of sodium borohydride
• The first mild, in situ, single-pot, high-yielding well-screened copper (II) salt-based catalyst system utilizing the hydrogen surrogacy of sodium borohydride for selective hydrogenation of a broad range of nitro substrates into the corresponding amine under habitancy of water or methanol like green solvents have been described. Moreover, this catalytic system can also activate various functional groups for hydride reduction within prompted time, with low catalyst-loading, without any requirement of high pressure or molecular hydrogen supply. Notably, this system explores a great potential to substitute expensive traditional hydrogenation methodologies and thus offers a greener and simple hydrogenative strategy in the field of organic synthesis.
• Kalola, Anirudhdha G.,Prasad, Pratibha,Mokariya, Jaydeep A.,Patel, Manish P.
• supporting information

  p. 3565 - 3589

  (2021/10/12)
• 

• Yeast supported gold nanoparticles: an efficient catalyst for the synthesis of commercially important aryl amines
• Candida parapsilosisATCC 7330 supported gold nanoparticles (CpGNP), prepared by a simple and green method can selectively reduce nitroarenes and substituted nitroarenes with different functional groups like halides (-F, -Cl, -Br), olefins, esters and nitriles using sodium borohydride. The product aryl amines which are useful for the preparation of pharmaceuticals, polymers and agrochemicals were obtained in good yields (up to >95%) using CpGNP catalyst under mild conditions. The catalyst showed high recyclability (≥10 cycles) and is a robust free flowing powder, stored and used after eight months without any loss in catalytic activity.
• Krishnan, Saravanan,Patel, Paresh N.,Balasubramanian, Kalpattu K.,Chadha, Anju
• supporting information

  p. 1915 - 1923

  (2021/02/06)
• 

• Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
• The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
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• Paragraph 0111-0118

  (2021/05/29)
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• A convenient Hofmann reaction of carboxamides and cyclic imides mediated by trihaloisocyanuric acids
• A simple, efficient and pot-economic approach in a single vessel has been developed for conversion of aromatic and aliphatic carboxamides into primary amines with one fewer carbom atom (Hofmann reaction) in 38–89 % yield by reacting with trichloro- or tribromoisocyanuric acid and sodium hydroxide in aqueous acetonitrile. Under the same reaction conditions, cyclic imides gave amino acids (69–83 %). The role of the trihaloisocyanuric acids is the in situ generation of N-haloamides, key-intermediates for the Hofmann reaction. The scalability of the methodology was demonstrated by a multigram-scale transformation of phthalimide into anthranilic acid in 77 % yield.
• Bastos, Gustavo A.,de Mattos, Marcio C.S.

• (2021/09/29)
• 

• Unlocking Amides through Selective C–N Bond Cleavage: Allyl Bromide-Mediated Divergent Synthesis of Nitrogen-Containing Functional Groups
• We report a new set of reactions based on the unlocking of amides through simple treatment with allyl bromide, creating a common platform for accessing a diverse range of nitrogen-containing functional groups such as primary amides, sulfonamides, primary amines, N-acyl compounds (esters, thioesters, amides), and N-sulfonyl esters. The method has potential industrial applicability, as demonstrated through gram-scale syntheses in batch and in a continuous flow system.
• Govindan, Karthick,Chen, Nian-Qi,Chuang, Yu-Wei,Lin, Wei-Yu

• p. 9419 - 9424

  (2021/11/30)
• 

• Method for preparing P-phenylenediamine
• The invention discloses a method for preparing high-purity p-phenylenediamine by reacting nitrobenzene with ammonia under the action of a catalyst to obtain 4-nitrosoaniline and 4-nitroaniline and then hydrogenating. Nitrobenzene and ammonia react under the action of a catalyst to generate 4-nitrosoaniline and 4-nitroaniline, the reaction selectivity is high, an ortho-position or meta-position product is not generated, and the yield is high. High-selectivity p-phenylenediamine can be obtained through catalytic hydrogenation of 4-nitrosoaniline and 4-nitroaniline, and the purity is high, so that the method is suitable for industrial production.
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• Paragraph 0044-0068

  (2021/01/24)
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• Method for synthesizing heteroatom- substituted aromatic compound from styrene compound
• The invention discloses a method for synthesizing a heteroatom-substituted aromatic compound from a styrene compound, which comprises the following steps of: mixing a styrene compound with a general formula (I) and a heteroatom-containing compound with a general formula (II), and reacting in the presence of an acid additive and an organic solvent to obtain a heteroatom-substituted compound with ageneral formula (III). According to the synthesis method disclosed by the invention, a large amount of styrene compounds are used as raw materials and react to generate aromatic amine or phenol compounds under the action of no metal catalysis; and compared with the traditional aromatic amine and phenol synthesis method, the method has the advantages of high yield, simple conditions, low waste discharge amount, no metal participation, simple reaction equipment, easiness in industrial production and the like.
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• Paragraph 0152-0155

  (2021/02/06)
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• Iridium-Triggered Allylcarbamate Uncaging in Living Cells
• Designing a metal catalyst that addresses the major issues of solubility, stability, toxicity, cell uptake, and reactivity within complex biological milieu for bioorthogonal controlled transformation reactions is a highly formidable challenge. Herein, we report an organoiridium complex that is nontoxic and capable of the uncaging of allyloxycarbonyl-protected amines under biologically relevant conditions and within living cells. The potential applications of this uncaging chemistry have been demonstrated by the generation of diagnostic and therapeutic agents upon the activation of profluorophore and prodrug in a controlled fashion within HeLa cells, providing a valuable tool for numerous potential biological and therapeutic applications.
• Gupta, Ajay,Gupta, Shalini,Mahawar, Pritam,Prasad, Puja,Sasmal, Pijus K.,Singh, Neelu
• supporting information

  p. 12644 - 12650

  (2021/09/06)
• 

• Cu-Catalyzed Cross-Coupling of Nitroarenes with Aryl Boronic Acids to Construct Diarylamines
• The development and study of a simple copper-catalyzed reaction of nitroarenes with aryl boronic acids to form diarylamines that uses phenyl silane as the stoichiometric terminal reductant is described. This cross-coupling reaction requires as little as 2 mol % of CuX and 4 mol % of diphosphine for success and tolerates a broad range of functional groups on either the nitroarene or the aryl boronic acid to afford the amine in good yield. Mechanistic investigations established that the cross-coupling reaction proceeds via a nitrosoarene intermediate and that copper is required to catalyze both the deoxygenation of the nitroarene to afford the nitrosoarene and C-NAr bond formation of the nitrosoarene with the aryl boronic acid.
• Guan, Xinyu,Zhu, Haoran,Driver, Tom G.

• p. 12417 - 12422

  (2021/10/12)
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• Immobilized Kallikrein Microreactor Based on Capillary Electrophoresis for Online Enzyme Kinetics Analysis and Inhibitor Screening
• In this study, an online capillary electrophoresis-based immobilized enzyme microreactor (CE-IMER) was developed for evaluating inhibitory activity of small-molecule compounds and tea polyphenol extracts on kallikrein (KLK). KLK was immobilized on the inner wall at the inlet of capillary to prepare the KLK-IMER with the aid of chitosan and glutaraldehyde. The immobilized KLK activity and other kinetic parameters were evaluated by measuring the peak area of hydrolysate of chromogenic substrate S-2302 (H-D-Pro-Phe-Arg-pNA). The Michaelis–Menten constant (Km) was determined to be 1.82?mM, and the half-maximal inhibitory concentration (IC50) and inhibition constant (Ki) of nicotinamide (positive control drug) were measured to be 12.07 and 4.31?mM, respectively. The negative control drug tinidazole (5.00?mM) had no inhibitory effect on KLK. Moreover, the activity of the immobilized KLK remained approximately 80.0% of the initial immobilized enzyme activity after 30 runs. The CE-IMER was applied to investigate the inhibitory activity of 10 small-molecule compounds and six tea polyphenol extracts on KLK. The results show that four small-molecule compounds (epicatechin gallate, epigallocatechin, epicatechin and isochlorogenic acid C) (0.25?mM) and six polyphenol extracts (Raw Pu-erh, Mingqian Mao Feng, Fuding white tea, Dark green tea, Biluochun and Black tea) (0.25?mg?mL?1) have high inhibitory activity on KLK. In addition, these four small-molecule compounds have binding energies below ? 5.0?kcal?mol?1 on KLK according to the molecular docking. In short, this study reports a time saving method (0.75?h) for KLK immobilization under mild conditions (25?°C). Graphic abstract: [Figure not available: see fulltext.]
• Chen, Guo-Ying,Chen, Hua,Hu, Yuan-Jia,Wang, Yuan,Yang, Feng-Qing,Zhang, Chun-Yan,Zhang, Hao,Zhao, Cong-Peng

• p. 1141 - 1150

  (2021/10/14)
• 

• A new ligand for copper-catalyzed amination of aryl halides to primary(hetero)aryl amines
• N,N′-Bis(3,5-dimethoxyphenyl)cyclopentane-1,1-dicarboxamide was found as a new ligand for copper-catalyzed amination of aryl iodides, bromides and chlorides to afford various primary (hetero)aryl amines. These reactions proceeded efficiently under mild conditions when inexpensive aqueous ammonia (28% NH3 in H2O) was used as the amino source.
• Chen, Dong,Dong, Xinrui,Jiang, Shang,Jiang, Sheng,Qiu, Yatao,Wu, Xiaoxing
• supporting information

  (2020/02/11)
• 

• CO-free, aqueous mediated, instant and selective reduction of nitrobenzeneviarobustly stable chalcogen stabilised iron carbonyl clusters (Fe3E2(CO)9, E = S, Se, Te)
• Highly stable and thermally robust iron chalcogenide carbonyl clusters Fe3E2(CO)9(E = S, Se or Te) have been explored for the reduction of nitrobenzene. A 15 min thermal heating of an aqueous solution of nitrobenzene and hydrazine hydrate in the catalytic presence of Fe3E2(CO)9(E = S, Se or Te) clusters yield average to excellent aniline transformations. Among the S, Se and Te based iron chalcogenised carbonyl clusters, the diselenide cluster was found to be most efficient and produce almost 90% yield of the desired amino product, the disulfide cluster was also found to be significantly active, produce the 85% yield of amino product, while the ditelluride cluster was not found to be active and produced only 49% yield of the desired product. The catalyst can be reused up to three catalytic cycles and it needs to be dried in an oven for one hour prior to reuse for the best results. The developed method is inexpensive, environmentally benign, does not require any precious metal or a high pressure of toxic CO gas and exclusively brings the selective reduction of the nitro group under feasible and inert free conditions.
• Joshi, Raj Kumar,Kumari, Sangeeta,Sharma, Charu,Soni, Aditi,Srivastava, Avinash Kumar

• p. 32516 - 32521

  (2020/09/17)
• 

• Selective Liquid Phase Hydrogenation of Aromatic Nitro Compounds in the Presence of Fe–Cu Nanoparticles
• Abstract: Fe–Cu bimetallic oxide nanoparticles supported on silica gel that catalyze the hydrogenation of nitrobenzene to aniline and of dinitrobenzenes to phenylenediamines under relatively mild reaction conditions (200°C, pH2 1.3 MPa, 4 h, and 700 rpm) are synthesized. The catalytic properties of supported bimetallic Fe–Cu catalysts depend on the synthesis procedure, sample composition, and conditions of thermal treatment. There is a synergistic effect of interaction between Cu and Fe in the hydrogenation of nitrobenzene, 1,3-dinitrobenzene, and 1,4-dinitrobenzene in the presence of a bimetallic Fe–Cu catalyst obtained via coprecipitation.
• Shesterkina,Strekalova,Kustov

• p. 1180 - 1183

  (2020/06/08)
• 

• Water-soluble gold nanoparticles: Recyclable catalysts for the reduction of aromatic nitro compounds in water
• A structure/catalytic activity study of water-soluble gold nanoparticles, stabilized by zwitterionic ligands derived from imidazolium salts, in the reduction of aromatic nitro compounds in pure water at different temperature, as well as their recyclabilit
• Correa, N. Mariano,Falcone, R. Darío,Monti, Gustavo A.,Moyano, Fernando,Silbestri, Gustavo F.

• p. 15065 - 15071

  (2020/05/06)
• 

• Heterogeneous photocatalysis of azides: Extending nitrene photochemistry to longer wavelengths
• The photodecomposition of azides to generate nitrenes usually requires wavelengths in the 300 nm region. In this study, we show that this reaction can be readily performed in the UVA region (368 nm) when catalyzed by Pd-decorated TiO2. In aqueous medium the reaction leads to amines, with water acting as the H source; however, in non-protic and non-nucleophilic media, such as acetonitrile, nitrenes recombine to yield azo compounds, while azirine-mediated trapping occurs in the presence of nucleophiles. The heterogeneous process facilitates catalyst separation while showing great chemoselectivity and high yields.
• Argüello, Juan E.,Lanterna, Anabel E.,Lemir, Ignacio D.,Scaiano, Juan C.
• supporting information

  p. 10239 - 10242

  (2020/10/02)
• 

• Mild deprotection of the: N-tert -butyloxycarbonyl (N -Boc) group using oxalyl chloride
• We report a mild method for the selective deprotection of the N-Boc group from a structurally diverse set of compounds, encompassing aliphatic, aromatic, and heterocyclic substrates by using oxalyl chloride in methanol. The reactions take place under room temperature conditions for 1-4 h with yields up to 90percent. This mild procedure was applied to a hybrid, medicinally active compound FC1, which is a novel dual inhibitor of IDO1 and DNA Pol gamma. A broader mechanism involving the electrophilic character of oxalyl chloride is postulated for this deprotection strategy. This journal is
• Awuah, Samuel G.,George, Nathaniel,Ofori, Samuel,Parkin, Sean

• p. 24017 - 24026

  (2020/07/23)
• 

• Cycloglutaramide-based ligand, synthetic method of ligand, application of ligand in coupling reaction for synthesizing arylamine derivative and catalytic system
• The invention discloses a cycloglutaramide-based ligand having a general formula I shown in the specification, a synthetic method of the ligand, an application of the ligand in a coupling reaction forsynthesizing an arylamine derivative, and a catalytic system. The compounds represented by the formula I can be used as a ligand in the coupling reaction of synthesizing the arylamine derivative by using an aryl halide under catalysis of copper, especially the coupling reaction of aryl halide and an amine source to form a C-N bond under catalysis. Under mild reaction conditions, the high-yield arylamine derivative is obtained, and the ligand has a simple structure, convenient preparation and a less use amount.
• -
• Paragraph 0106; 0107; 0108; 0109; 0110

  (2020/03/12)
• 

• Isonitrile-responsive and bioorthogonally removable tetrazine protecting groups
• In vivo compatible reactions have a broad range of possible applications in chemical biology and the pharmaceutical sciences. Here we report tetrazines that can be removed by exposure to isonitriles under very mild conditions. Tetrazylmethyl derivatives are easily accessible protecting groups for amines and phenols. The isonitrile-induced removal is rapid and near-quantitative. Intriguingly, the deprotection is especially effective with (trimethylsilyl)methyl isocyanide, and serum albumin can catalyze the elimination under physiological conditions. NMR and computational studies revealed that an imine-tautomerization step is often rate limiting, and the unexpected cleavage of the Si-C bond accelerates this step in the case with (trimethylsilyl)methyl isocyanide. Tetrazylmethyl-removal is compatible with use on biomacromolecules, in cellular environments, and in living organisms as demonstrated by cytotoxicity experiments and fluorophore-release studies on proteins and in zebrafish embryos. By combining tetrazylmethyl derivatives with previously reported tetrazine-responsive 3-isocyanopropyl groups, it was possible to liberate two fluorophores in vertebrates from a single bioorthogonal reaction. This chemistry will open new opportunities towards applications involving multiplexed release schemes and is a valuable asset to the growing toolbox of bioorthogonal dissociative reactions.
• Tu, Julian,Svatunek, Dennis,Parvez, Saba,Eckvahl, Hannah J.,Xu, Minghao,Peterson, Randall T.,Houk,Franzini, Raphael M.

• p. 169 - 179

  (2019/12/30)
• 

• A polyamine dendritic polymer-copper complex: A reusable catalyst for the additive-free amination of aryl bromides, and iodides
• A porphyrin-initiated amine-functionalized polyepichlorohydrin dendritic polymer (PPECH-Amine) was effectively synthesized, and its water-soluble copper complex (PPECH-Amine-Cu) was developed by treating it with copper acetate. PPECH-Amine and PPECH-Amine-Cu were characterised by different spectroscopic and microscopic techniques. PPECH-Amine-Cu was identified as a reusable catalyst for the amination of bromo- and iodo-benzene derivatives in aqueous media. Due to the presence of residual amino groups in the PPECH-Amine-Cu catalyst, the protocol does not need any additional base additive, as ammonia itself acts as a base and a coupling partner. Due to the good water-soluble nature of this catalyst, it can be easily separated and reused up to six reaction cycles without any loss in its activity.
• Avudaiappan,Palmurukan,Unnikrishnan,Sreekumar

• p. 1477 - 1484

  (2020/02/05)
• 

• Phenazine-Based Donor Acceptor Systems as Organic Photocatalysts for "metal-free" C-N/C-C Cross-Coupling
• With an aim to achieve a balance between ground-state and excited-state reduction potential of donor acceptor systems for efficient C-N/C-C cross-coupling, a series of donor acceptor systems DA1-DA4 have been synthesized by varying the donor strength and connecting positions. With an increase in donor strength, systematic elevation in the ground-state reduction potential and decrease in the HOMO-LUMO gap was observed. Interestingly, all the derivatives DA1-DA4 could catalyze the C-N bond formation reaction between activated aryl halides and amines at low catalytic loading under metal-free conditions without the need of any external base upon irradiation with white LED. A balance was realized in the case of derivative DA2, which exhibits high efficiency in C-N couplings. Different control experiments support the validity of the energy as well as electron transfer pathways in the visible light-mediated C-N bond formation. This study further reveals the potential of derivative DA1 in "metal-free"Sonogashira coupling involving activated aryl halides which is attributed to its high excited-state reduction potential.
• Deol, Harnimarta,Singh, Gurpreet,Kumar, Manoj,Bhalla, Vandana

• p. 11080 - 11093

  (2020/10/12)
• 

• Modular AND Gate-Controlled Delivery Platform for Tumor Microenvironment Specific Activation of Protein Activity
• Protein therapeutics have inspired intensive research interest in a variety of realms. It is still urgently required to avoid premature or unexpected activation of therapeutic proteins to achieve great specificity for therapy. Herein, we reported a modula
• Ju, Enguo,Wang, Faming,Wang, Zhenzhen,Liu, Chaoying,Dong, Kai,Pu, Fang,Ren, Jinsong,Qu, Xiaogang
• supporting information

  p. 7573 - 7577

  (2020/06/08)
• 

• Triazolecarbaldehyde Reagents for One-Step N-Terminal Protein Modification
• Site-specific modification of peptides and proteins is a key aspect of protein engineering. We developed a method for modification of the N terminus of proteins using 1H-1,2,3-triazole-4-carbaldehyde (TA4C) derivatives, which can be prepared in one step. The N-terminal specific labeling of bioactive peptides and proteins with the TA4C derivatives proceeds under mild reaction conditions in excellent conversion (angiotensin I: 92 %, ribonuclease A: 90 %). This method enables site-specific conjugation of various functional molecules such as fluorophores, biotin, and polyethylene glycol attached to the triazole ring to the N terminus. Furthermore, a functional molecule modified with a primary amine moiety can be directly converted into a TA4C derivative through a Dimroth rearrangement reaction with 1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbaldehyde. This method can be used to obtain N-terminal-modified proteins via only two steps: 1) convenient preparation of a TA4C derivative with a functional group and 2) modification of the N terminus of the protein with the TA4C derivative.
• Onoda, Akira,Inoue, Nozomu,Sumiyoshi, Eigo,Hayashi, Takashi

• p. 1274 - 1278

  (2020/01/25)
• 

• Synthesis of azobenzenes with high reactivity towards reductive cleavage: Enhancing the repertoire of hypersensitive azobenzenes and examining their dissociation behavior
• Trifluoromethyl (CF3), cyano (CN), and nitro (NO2) groups were demonstrated to be effective acceptors in the molecular design of triple-donor/acceptor-based hypersensitive azobenzenes. The synthesis of these reactive scaffolds requires only two steps with overall yields ranging from 70 to 73percent. UV–Vis absorption spectroscopy indicated that in all cases, a few seconds of exposure to mild reducing conditions is sufficient for complete cleavage of the azo bond. Liquid chromatography coupled with mass spectrometry (LC-MS) established the formation of two aniline fragments in the case of the CF3 and CN-substituted azobenzenes. In the case of the NO2-substituted compound, however, partial reduction of the nitro group results in the formation of three different anilines.
• Eom, Taejun,Khan, Anzar
• supporting information

  (2020/05/19)
• 

• A Hydroxyquinoline-Based Unnatural Amino Acid for the Design of Novel Artificial Metalloenzymes
• We have examined the potential of the noncanonical amino acid (8-hydroxyquinolin-3-yl)alanine (HQAla) for the design of artificial metalloenzymes. HQAla, a versatile chelator of late transition metals, was introduced into the lactococcal multidrug-resista
• Drienovská, Ivana,Scheele, Remkes A.,Gutiérrez de Souza, Cora,Roelfes, Gerard

• p. 3077 - 3081

  (2020/07/24)
• 

• Investigations of conformational structures and activities of trypsin and pepsin affected by food colourant allura red
• Herein, binding interactions of food colourant allura red (AR) with trypsin and pepsin were comparably investigated for deep revelations of conformational structures and activities of proteinases affected by food colourant. Various results indicated that
• Huang, Shan,Li, Haimei,Liang, Jiandan,Luo, Huajian,Xiao, Qi,Yang, Jing

• (2020/10/02)
• 

• Base promoted peroxide systems for the efficient synthesis of nitroarenes and benzamides
• A useful and efficient approach for the synthesis of nitroarenes from several aromatic amines (including heterocycles) using peroxide and base has been developed. This oxidative reaction is very easy to handle and afforded the products in good yields. Formation of benzamides from benzylamine was also successfully carried out with this metal-free catalytic system in good to excellent yields.
• Gupta, Sampa,Ansari, Alisha,Sashidhara, Koneni V.
• supporting information

  (2019/09/07)
• 

• Copper(ii)-catalyzed c-n coupling of aryl halides and n-nucleophiles promoted by quebrachitol or diethylene glycol
• Herein, we report the natural ligand quebrachitol (QCT) as a promoter for a Cu(II) catalyst, which is highly effective for N-Arylation of various amines and related aryl halides. A series of diarylamine derivatives were obtained in high yields by using diethylene glycol (DEG) as both ligand and solvent. The C-N coupling reactions proceed under mild conditions and exhibit good functional group tolerance.
• Chen, Guoliang,Chen, Yuanguang,Du, Fangyu,Fu, Yang,Wu, Ying,Zhou, Qifan
• supporting information

  p. 2161 - 2168

  (2019/11/25)
• 

• A green and recyclable ligand-free copper (I) catalysis system for amination of halonitrobenzenes in aqueous ammonia solution
• The amination of halonitrobenzenes is an important reaction to produce the corresponding nitroanilines. Direct amination of p-chloronitrobenzene (p-CNB) to p-nitroaniline (p-NAN) with aqueous NH3 solution was investigated over various transition metal salts in the absence of ligand, inorganic base and organic solvent. It was found that CuI is the most effective catalyst with respect to p-CNB conversion, p-NAN selectivity (≈ 100%) and the post-reaction separation and recycling. A high p-NAN yield of 97% could be obtained at 200 °C in 6.5 h with molar ratios of NH3/p-CNB and CuI/p-CNB of 21 and 0.1, respectively. A possible reaction mechanism was proposed, in which NH3 was not only a substrate but also a ligand to coordinate with CuI and formed a water-soluble Cu complex, and then it started the catalytic cycle. The influence of reaction variables such as NH3 concentration, CuI concentration, temperature and time on the p-CNB conversion and the p-NAN selectivity was examined. At room temperature the desired product of p-NAN is insoluble in water but the Cu complex catalyst is water-soluble and so the aqueous phase including the catalyst and NH3 can be easily separated and reused for the subsequent reaction runs. The green and sustainable system is effective for the conversion of diverse halonitrobenzenes to nitroanilines.
• Li, Yan,Shi, Ruhui,Lin, Weiwei,Cheng, Haiyang,Zhang, Chao,Arai, Masahiko,Zhao, Fengyu

• (2019/06/18)
• 

• Effect of linker and metal on photoreduction and cascade reactions of nitroaromatics by M-UiO-66 metal organic frameworks
• The use of metal organic frameworks (MOFs) as photocatalysts is a promising and growing area of research. Given the diverse architectures, linkers, and metals, it is important to understand their effects on catalysis. Herein we compare six MOFs of the UiO-66 family towards photocatalytic reduction of nitro-aromatics to anilines. These MOFs differ in metal identity (Hf, Zr) and linker, and hence this systematic study provides insights to developing next generation MOFs. We found that Hf-based MOFs are superior to the more commonly studied Zr-analogues. Moreover, the linker identity also impact the photocatalysis, with pyridine-based linkers out-performing aniline based linkers and those that lack an embedded basic site. The MOFs studied have unique selectivities for the photoreduction and also allow for the one-pot synthesis of imines from aromatic aldehydes and nitro-aromatics.
• Elkin,Saouma
• supporting information

  (2019/08/30)
• 

• Metal-free chemoselective reduction of nitroaromatics to anilines via hydrogen transfer strategy
• A novel protocol for chemoselective reduction of aromatic nitro compounds to aromatic amines has been established. The metal-free reduction goes through a hydrogen transfer process. Various easily reducible functional groups can be well tolerated under the optimized reaction conditions.
• Shuai, Qi,Li, Jun,Zhao, Feng,Su, Weike,Deng, Guojun

• p. 965 - 975

  (2019/04/13)
• 

• Synthesis method of paranitroaniline
• The invention discloses a continuous synthesis method of paranitroaniline. The continuous synthesis method comprises the following steps: 1) preparing ammonia water by using an ammonia water preparation unit, respectively and continuously inputting the pr
• -
• Paragraph 0027-0034

  (2019/11/12)
• 

• MnCo2O4+: X nanowire arrays grown on carbon sponge: Improved electrochemical and catalytic performances
• MnCo2O4+x nanowire arrays have been successfully grown on carbon sponge (CS) via a simple hydrothermal route with sequential thermal treatment, employing CoSO4·7H2O, MnSO4·H2O and urea as t
• Li, Shifeng,Wang, Jie,Wang, Meifang,Ni, Yonghong

• p. 403 - 410

  (2019/01/21)
• 

• Excellent photocatalytic reduction of nitroarenes to aminoarenes by BiVO4 nanoparticles grafted on reduced graphene oxide (rGO/BiVO4)
• A novel heterogeneous composite material based on reduced graphene oxide (rGO) and bismuth vanadate (BiVO4) was prepared and characterized by various techniques such as powder XRD, HRTEM, EADX, UV–Vis-DRS, FT-IR, Raman, BET and XPS analyses. The characterization results reveal that the rGO well decorated by BiVO4. The electrochemical impedance spectroscopy (EIS) shows the increasing of charge transfer of rGO/BiVO4 in presence of light irradiation. In this research, the pure BiVO4 and rGO/BiVO4 composite have been explored for photocatalytic reduction of nitroarenes. Among the prepared nanocomposites, rGO loaded with 10% BiVO4 catalyst (noted as rGO/BiVO4–10%) shows the best performance for the photo-reduction of various nitroaromatic molecules to their corresponding amine compounds under visible-light irradiation at room temperature. The catalyst exhibited in particular excellent photocatalytic activity for the conversion of 1,4-dinitrobenzene to 4-nitroanilline (100% conversion) in 20?min, 4-chloronitrobenzene to 4-chloroaniline and 2-nitrophenol to 2-aminophenol (100% conversion) in only 30?min. In addition, the conversion of 4-bromonitrobenzene, 4-iodonitrobenzene to their corresponding amine compounds (100% conversion) was achieved in 60?min. The catalyst was recovered for several times and reused without decreasing of its efficiency.
• Azad, Roya,Bezaatpour, Abolfazl,Amiri, Mandana,Eskandari, Habibollah,Nouhi, Sima,Taffa, Dereje H.,Wark, Michael,Boukherroub, Rabah,Szunerits, Sabine

• (2019/07/03)
• 

• Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
• The Br?nsted acid-catalyzed synthesis of primary amines from acetyl arenes and alkanes with C-C bond cleavage is described. Although the conversion from an acetyl group to amine has traditionally required multiple steps, the method described herein, which uses an oxime reagent as an amino group source, achieves the transformation directly via domino transoximation/Beckmann rearrangement/Pinner reaction. The method was also applied to the synthesis of γ-aminobutyric acids, such as baclophen and rolipram.
• Hyodo, Kengo,Hasegawa, Genna,Maki, Hiroya,Uchida, Kingo
• supporting information

  p. 2818 - 2822

  (2019/04/25)
• 

• PRODUCTION METHOD OF PRIMARY AMINE COMPOUND
• PROBLEM TO BE SOLVED: To provide a simple production method of a primary amine compound unnecessary for complicated procedures and toxic sodium azide or the like. SOLUTION: A production method of a primary amine compound includes a step for reacting a ketone compound and an oxime compound in the presence of alcohol and an acid catalyst. Preferably, the acid catalyst is hydrochloric acid, sulfuric acid, methanesulfonic acid, camphorsulfonic acid, a tosyl acid hydrate, trifluoromethane sulfonic acid or a boron trifluoride diethyl ether complex. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
• -
• Paragraph 0029

  (2019/09/20)
• 

• Plasmonically Coupled Nanoreactors for NIR-Light-Mediated Remote Stimulation of Catalysis in Living Cells
• Artificial nanoreactors that can facilitate catalysis in living systems on-demand with the aid of a remotely operable and biocompatible energy source are needed to leverage the chemical diversity and expediency of advanced chemical synthesis in biology and medicine. Here, we designed and synthesized plasmonically integrated nanoreactors (PINERs) with highly tunable structure and NIR-light-induced synergistic function for efficiently promoting unnatural catalytic reactions inside living cells. We devised a synthetic approach toward PINERs by investigating the crucial role of metal-tannin coordination polymer nanofilm - the pH-induced decomplexation-mediated phase-transition process - for growing arrays of Au-nanospheroid-units, constructing a plasmonic corona around the proximal and reactant-accessible silica-compartmentalized catalytic nanospace. Owing to the extensive plasmonic coupling effect, PINERs show strong and tunable optical absorption in the visible to NIR range, ultrabright plasmonic light scattering, controllable thermoplasmonic effect, and remarkable catalysis; and, upon internalization by living cells, PINERs are highly biocompatible and demonstrate dark-field microscpy-based bioimaging features. Empowered with the synergy between plasmonic and catalytic effects and reactant/product transport, facilitated by the NIR-irradiation, PINERs can perform intracellular catalytic reactions with dramatically accelerated rates and efficiently synthesize chemically activated fluorescence-probes inside living cells.
• Kumar, Amit,Kumar, Sumit,Kumari, Nitee,Lee, Seon Hee,Han, Jay,Michael, Issac J.,Cho, Yoon-Kyoung,Lee, In Su

• p. 977 - 990

  (2019/01/15)
• 

• Amination of Aromatic Halides and Exploration of the Reactivity Sequence of Aromatic Halides
• A base-promoted amination of aromatic halides has been developed using a limited amount of dimethylformamide (DMF) or amine as an amino source. Various aryl halides, including F, Cl, Br, and I, have been successfully aminated in good to excellent yields. Although the amination of aromatic halides with amines or DMF is usually considered as an aromatic nucleophilic substitution (SNAr) process, and the reactivity of an aromatic halide is F > Cl > Br > I, the reactivity of aromatic halides in this system was found to be I > Br a‰ F > Cl. This protocol also showed a good regioselectivity for multihalogenated aromatics. This protocol is valuable for industrial application due to the simplicity of operation, the unrestricted availability of amino sources and aromatic halides, transition metal-free conditions, no requirement for solvent, and scalability.
• Yang, Chu,Zhang, Feng,Deng, Guo-Jun,Gong, Hang

• p. 181 - 190

  (2019/01/10)
• 

• Organelle-Targeted BODIPY Photocages: Visible-Light-Mediated Subcellular Photorelease
• Photocaging facilitates non-invasive and precise spatio-temporal control over the release of biologically relevant small- and macro-molecules using light. However, sub-cellular organelles are dispersed in cells in a manner that renders selective light-irradiation of a complete organelle impractical. Organelle-specific photocages could provide a powerful method for releasing bioactive molecules in sub-cellular locations. Herein, we report a general post-synthetic method for the chemical functionalization and further conjugation of meso-methyl BODIPY photocages and the synthesis of endoplasmic reticulum (ER)-, lysosome-, and mitochondria-targeted derivatives. We also demonstrate that 2,4-dinitrophenol, a mitochondrial uncoupler, and puromycin, a protein biosynthesis inhibitor, can be selectively photoreleased in mitochondria and ER, respectively, in live cells by using visible light. Additionally, photocaging is shown to lead to higher efficacy of the released molecules, probably owing to a localized and abrupt release.
• Kand, Dnyaneshwar,Pizarro, Lorena,Angel, Inbar,Avni, Adi,Friedmann-Morvinski, Dinorah,Weinstain, Roy
• supporting information

  p. 4659 - 4663

  (2019/03/26)
• 

• A convenient room temperature ipso-nitration of arylboronic acid catalysed by molecular iodine using zirconium oxynitrate as nitrating species: An experimental and theoretical investigation
• A simple and convenient protocol has been developed for ipso-nitration of arylboronic acid catalysed by molecular iodine at room temperature, using zirconium oxynitrate as the nitrating species. The protocol is applicable to electronically diverse aryl- and heteroarylboronic acid moieties under mild reaction conditions with good to excellent isolated yields. Furthermore, a theoretical investigation has been performed for the same reaction, and reaction profiles are modelled using modern density functional theory (DFT). DFT-based results support the experimentally observed results.
• Mahanta, Abhijit,Gour, Nanda Kishor,Sarma, Plaban Jyoti,Borah, Raju Kumar,Raul, Prasanta Kumar,Deka, Ramesh Chandra,Thakur, Ashim Jyoti,Bora, Utpal

• (2019/05/15)
• 

• From alkylarenes to anilines via site-directed carbon–carbon amination
• Anilines are fundamental motifs in various chemical contexts, and are widely used in the industrial production of fine chemicals, polymers, agrochemicals and pharmaceuticals. A recent development for the synthesis of anilines uses the primary amination of C–H bonds in electron-rich arenes. However, there are limitations to this strategy: the amination of electron-deficient arenes remains a challenging task and the amination of electron-rich arenes has a limited control over regioselectivity—the formation of meta-aminated products is especially difficult. Here we report a site-directed C–C bond primary amination of simple and readily available alkylarenes or benzyl alcohols for the direct and efficient preparation of anilines. This chemistry involves a novel C–C bond transformation and offers a versatile protocol for the synthesis of substituted anilines. The use of O2 as an environmentally benign oxidant is demonstrated, and studies on model compounds suggest that this method may also be used for the depolymerization of lignin.
• Liu, Jianzhong,Qiu, Xu,Huang, Xiaoqiang,Luo, Xiao,Zhang, Cheng,Wei, Jialiang,Pan, Jun,Liang, Yujie,Zhu, Yuchao,Qin, Qixue,Song, Song,Jiao, Ning

• p. 71 - 77

  (2018/11/10)
• 

• Aromatic amine compound synthesis method
• The invention discloses an aromatic amine compound synthesis method which is characterized in that the method is implemented according to any of two methods. The first method includes the steps: mixing an alkyl aromatic compound with a general formula (I) and a nitrogen-containing compound with a general formula (II); performing reaction on mixture under an oxidizing agent and an organic solvent to obtain an aromatic amine compound with a general formula (III). The second method includes the steps: mixing an aromatic alcohol derivative with a general formula (I') and the nitrogen-containing compound with the general formula (II); performing reaction on mixture under an acid additive and an organic solvent to prepare the aromatic amine compound with the general formula (III). According to the method, a lot of alkyl aromatic compounds or aromatic alcohol derivatives firstly serve as raw materials, and the raw materials are reacted to generate the aromatic amine compound without the action of metal catalysis. Compared with a traditional synthesis method, the synthesis method has the advantages that the method is high in yield and simple in condition, waste discharging amount is less,metal participation is omitted, a reaction device is simple, industrial production is easily achieved and the like. The method has a wide application prospect.
• -
• Paragraph 0129-0131

  (2019/01/23)
• 

• Divergent Late-Stage (Hetero)aryl C?H Amination by the Pyridinium Radical Cation
• (Hetero)arylamines constitute some of the most prevalent functional molecules, especially as pharmaceuticals. However, structurally complex aromatics currently cannot be converted into arylamines, so instead, each product isomer must be assembled through a multistep synthesis from simpler building blocks. Herein, we describe a late-stage aryl C?H amination reaction for the synthesis of complex primary arylamines that other reactions cannot access directly. We show and rationalize through a mechanistic analysis the reasons for the wide substrate scope and the constitutional diversity of the reaction, which gives access to molecules that would not have been readily available otherwise.
• Ham, Won Seok,Hillenbrand, Julius,Jacq, Jér?me,Genicot, Christophe,Ritter, Tobias
• supporting information

  p. 532 - 536

  (2019/01/04)
• 

• Copper-catalyzed arene amination in pure aqueous ammonia
• A simple protocol for copper-catalyzed arene amination using aqueous ammonia without any additional ligands and organic coordinating solvents has been developed. The reaction pathway via a Cu(i)/Cu(iii) mechanism is proposed based on the results of control experiments as well as DFT calculations.
• Takagi, Mio,Watanabe, Ayako,Murata, Shigeo,Takita, Ryo
• supporting information

  p. 1791 - 1795

  (2019/02/20)
•