- Bridging the gap between electrochemical and organometallic activation: Benzyl chloride reduction at silver cathodes
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Integration of voltammetry, surface-enhanced Raman spectroscopy (SERS), and density functional theory (DFT) has allowed unraveling the mechanistic origin of the exceptional electrocatalytic properties of silver cathodes during the reduction of benzyl chloride. At inert electrodes the initial reduction proceeds through a concerted direct electron transfer yielding a benzyl radical as the first intermediate. Conversely, at silver electrodes it involves an uphill preadsorption of benzyl chloride onto the silver cathode. Reduction of this adduct affords a species tentatively described as a distorted benzyl radical anion stabilized by the silver surface. This transient species rapidly evolves to yield ultimately a benzyl radical bound onto the silver surface, the latter being reduced into a benzyl-silver anionic adduct which eventually dissociates into a free benzyl anion at more negative potentials. Within this framework, the exceptional electrocatalytic properties of silver cathodes stem from the fact that they drastically modify the mechanism of the 2e-reduction pathway through a direct consequence of the electrophilicity of silver cathode surfaces toward organic halides. This mechanism contrasts drastically with any of those tentatively invoked previously, and bridges classical electroreduction mechanisms and oxidative additions similar to those occurring during organometallic homogeneous activation of organic halides by low-valent transition-metal complexes.
- Huang, Yi-Fan,Wu, De-Yin,Wang, An,Ren, Bin,Rondinini, Sandra,Tian, Zhong-Qun,Amatore, Christian
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Read Online
- Enantioselective hydrogenation of diaryl-substituted α,β-unsaturated nitriles
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α,β-Unsaturated nitriles can be hydrogenated with enantioselectivities up to 88% ee using chiral ruthenium-diphenylphosphino bisaryl and bisheteroaryl complexes such as ruthenium(II)-BINAP and ruthenium(II)-BINP. Mechanistic investigations indicate that conversion is accelerated by electron-rich ligands and that an additional coordinative group needs be present in order to promote conversion. The chiral products are useful building blocks for the synthesis of histamine H2 agonists of the arpromidine type.
- Wabnitz, Tobias C.,Rizzo, Simona,G?tte, Carsten,Buschauer, Armin,Benincori, Tiziana,Reiser, Oliver
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Read Online
- From Stoichiometric Reagents to Catalytic Partners: Selenonium Salts as Alkylating Agents for Nucleophilic Displacement Reactions in Water
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The ability of chalcogenium salts to transfer an electrophilic moiety to a given nucleophile is well known. However, up to date, these reagents have been used in stoichiometric quantities, producing a substantial amount of waste as byproducts of the reaction. In this report, we disclose further investigation of selenonium salts as S-adenosyl-L-methionine (SAM) surrogates for the alkylation of nucleophiles in aqueous solutions. Most importantly, we were able to convert the stoichiometric process to a catalytic system employing as little as 10 mol % of selenides to accelerate the reaction between benzyl bromide and other alkylating agents with sodium cyanide in water. Probe experiments including 77Se NMR and HRMS of the reaction mixture have unequivocally shown the presence of the selenonium salt in the reaction mixture. (Figure presented.).
- Martins, Nayara Silva,ángel, Alix Y. Bastidas,Anghinoni, Jo?o M.,Lenard?o, Eder J.,Barcellos, Thiago,Alberto, Eduardo E.
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supporting information
p. 87 - 93
(2021/11/03)
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- Palladium-catalyzed synthesis of nitriles from N-phthaloyl hydrazones
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The Pd-catalyzed transformation of N-phthaloyl hydrazones into nitriles involving the cleavage of an N-N bond is reported. The use of N-heterocyclic carbene as a ligand is essential for the success of the reaction. N-Phthaloyl hydrazones prepared from aromatic aldehydes or cyclobutanones are applicable to this transformation, which gives aryl or alkenyl nitriles, respectively.
- Ano, Yusuke,Chatani, Naoto,Higashino, Masaya,Yamada, Yuki
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supporting information
p. 3799 - 3802
(2022/04/07)
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- Method for dehydrating primary amide into nitriles under catalysis of cobalt
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The invention provides a method for dehydrating primary amide into nitrile. The method comprises the following steps: mixing primary amide (II), silane, sodium triethylborohydride, aminopyridine imine tridentate nitrogen ligand cobalt complex (I) and a reaction solvent under the protection of inert gas, carrying out reacting at 60-100 DEG C for 6-24 hours, and post-treating reaction liquid to obtain a nitrile compound (III). According to the invention, an effective method for preparing nitrile compounds by cobalt-catalyzed primary amide dehydration reaction by using the novel aminopyridine imine tridentate nitrogen ligand cobalt complex catalyst is provided; and compared with existing methods, the method has the advantages of simple operation, mild reaction conditions, wide application range of reaction substrates, high selectivity, stable catalyst, high efficiency, and relatively high practical application value in synthesis.
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Paragraph 0087-0089
(2021/06/21)
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- Reduction of Electron-Deficient Alkenes Enabled by a Photoinduced Hydrogen Atom Transfer
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Direct hydrogen atom transfer from a photoredox-generated Hantzsch ester radical cation to electron-deficient alkenes has enabled the development of an efficient formal hydrogenation under mild, operationally simple conditions. The HAT-driven mechanism is supported by experimental and computational studies. The reaction is applied to a variety of cinnamate derivatives and related structures, irrespective of the presence of electron-donating or electron-withdrawing substituents in the aromatic ring and with good functional group compatibility. (Figure presented.).
- Larionova, Natalia A.,Ondozabal, Jun Miyatake,Cambeiro, Xacobe C.
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supporting information
p. 558 - 564
(2020/12/07)
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- Selective oxidation of alcohols to nitriles with high-efficient Co-[Bmim]Br/C catalyst system
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An efficient method for catalyzing the ammoxidation of aromatic alcohols to aromatic nitriles was developed, in which a new heterogeneous catalyst based on transition metal elements was employed, the new catalyst was named Co-[Bmim]Br/C-700 and then characterized by X-ray photo-electronic spectroscopy, transmission electron microscope and X-ray diffraction. The reaction was carried out by two consecutive dehydrogenations under the catalysis of Co-[Bmim]Br/C-700, which catalytically oxidized the alcohol to the aldehyde, and then the aldehyde was subjected to ammoxidation to the nitrile. The catalyst system was suitable for a wide range of substrates and nitriles obtained in high yields, especially, the conversion rate of benzyl alcohol, 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol and 4-nitrobenzyl alcohol reached 100%. The substitution of ammonia and oxygen for toxic cyanide to participate in the reaction accords with the theory of green chemistry.
- Xia, Yu-Yan,Lv, Qing-Yang,Yuan, Hua,Wang, Jia-Yi
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p. 3957 - 3964
(2021/04/09)
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- A Titanium-Catalyzed Reductive α-Desulfonylation
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A titanium(III)-catalyzed desulfonylation gives access to functionalized alkyl nitrile building blocks from α-sulfonyl nitriles, circumventing traditional base-mediated α-alkylation conditions and strong single electron donors. The reaction tolerates numerous functional groups including free alcohols, esters, amides, and it can be applied also to the α-desulfonylation of ketones. In addition, a one-pot desulfonylative alkylation is demonstrated. Preliminary mechanistic studies indicate a catalyst-dependent mechanism involving a homolytic C?S cleavage.
- Kern, Christoph,Selau, Jan,Streuff, Jan
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p. 6178 - 6182
(2021/03/16)
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- Nickel/Cobalt-Catalyzed Reductive Hydrocyanation of Alkynes with Formamide as the Cyano Source, Dehydrant, Reductant, and Solvent
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A Ni/Co co-catalyzed reductive hydrocyanation of various alkynes was developed for the production of saturated nitriles. Hydrocyanic acid is generated in situ from safe and readily available formamide. Formamide played multiple roles as a cyano source, dehydrant, and reductant for the NiII pre-catalyst and vinyl nitriles, along with acting as the co-solvent in this reaction. Detailed mechanistic investigation supported a pathway via hydrocyanation of C≡C bond and the subsequent reduction of C=C bond. Wide substrate scope, the employment of a cheap and stable nickel salt as pre-catalyst, a safe cyano source and convenient experimental operation render this hydrocyanation practical for the laboratory synthesis of saturated nitriles. (Figure presented.).
- Zhang, Jin,Luo, Cui-Ping,Yang, Luo
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supporting information
p. 283 - 288
(2020/12/01)
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- Arylketones as Aryl Donors in Palladium-Catalyzed Suzuki-Miyaura Couplings
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Herein, we report the arylation, alkylation, and alkenylation of aryl ketones via a palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. The use of the pyridine-oxazoline ligand is the key to the cleavage of the unstrained C-C bond. The late-stage arylation of aryl ketones derived from drugs and natural products demonstrated the synthetic utility of this protocol.
- Wang, Zhen-Yu,Ma, Biao,Xu, Hui,Wang, Xing,Zhang, Xu,Dai, Hui-Xiong
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supporting information
p. 8291 - 8295
(2021/11/13)
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- Hydrosilylative reduction of primary amides to primary amines catalyzed by a terminal [Ni-OH] complex
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A terminal [Ni-OH] complex1, supported by triflamide-functionalized NHC ligands, catalyzes the hydrosilylative reduction of a range of primary amides into primary amines in good to excellent yields under base-free conditions with key functional group tolerance. Catalyst1is also effective for the reduction of a variety of tertiary and secondary amides. In contrast to literature reports, the reactivity of1towards amide reduction follows an inverse trend,i.e., 1° amide > 3° amide > 2° amide. The reaction does not follow a usual dehydration pathway.
- Bera, Jitendra K.,Pandey, Pragati
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supporting information
p. 9204 - 9207
(2021/09/20)
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- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
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Paragraph 0034-0039; 0273-0278
(2020/09/16)
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- SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
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A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.
- Ding, Chengrong,Ge, Shuting,Wei, Junjie,Zhang, Guofu,Zhao, Yiyong
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p. 17288 - 17292
(2020/05/18)
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- Metal-free dehydrosulfurization of thioamides to nitriles under visible light
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A visible light-mediated, metal-free dehydrosulfurization reaction of thioamides to nitriles is described. This reaction features high yields, mild reaction conditions, and the use of a cheap organic dye as the photoredox catalyst and air as the oxidant.
- Xu, Tianxiao,Cao, Tianpeng,Feng, Qingyuan,Huang, Shenlin,Liao, Saihu
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p. 5151 - 5153
(2020/05/26)
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- Hydrogenation reaction method
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The invention relates to a hydrogenation reaction method, and belongs to the technical field of organic synthesis. The hydrogenation reaction method provided by the invention comprises the following steps: carrying out a hydrogen transfer reaction on a hydrogen acceptor compound, pinacol borane and a catalyst in a solvent in the presence of proton hydrogen, so that the hydrogen acceptor compound is subjected to a hydrogenation reaction; the catalyst is one or more than two of a palladium catalyst, an iridium catalyst and a rhodium catalyst; the hydrogen acceptor compound comprises one or morethan two functional groups of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, nitryl, carbon-nitrogentriple bonds and epoxy. The method is mild in reaction condition, easy to operate, high in yield, short in reaction time, wide in substrate application range, suitable for carbon-carbon double bonds,carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, nitryl, carbon-nitrogen triple bonds and epoxy functional groups, good in selectivity and high in reaction specificity.
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Paragraph 0034; 0125-0128
(2020/05/14)
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- Generalized Chemoselective Transfer Hydrogenation/Hydrodeuteration
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A generalized, simple and efficient transfer hydrogenation of unsaturated bonds has been developed using HBPin and various proton reagents as hydrogen sources. The substrates, including alkenes, alkynes, aromatic heterocycles, aldehydes, ketones, imines, azo, nitro, epoxy and nitrile compounds, are all applied to this catalytic system. Various groups, which cannot survive under the Pd/C/H2 combination, are tolerated. The activity of the reactants was studied and the trends are as follows: styrene'diphenylmethanimine'benzaldehyde'azobenzene'nitrobenzene'quinoline'acetophenone'benzonitrile. Substrates bearing two or more different unsaturated bonds were also investigated and transfer hydrogenation occurred with excellent chemoselectivity. Nano-palladium catalyst in situ generated from Pd(OAc)2 and HBPin extremely improved the TH efficiency. Furthermore, chemoselective anti-Markovnikov hydrodeuteration of terminal aromatic olefins was achieved using D2O and HBPin via in situ HD generation and discrimination. (Figure presented.).
- Wang, Yong,Cao, Xinyi,Zhao, Leyao,Pi, Chao,Ji, Jingfei,Cui, Xiuling,Wu, Yangjie
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supporting information
p. 4119 - 4129
(2020/08/10)
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- Design, synthesis and biological evaluation of 8-(2-amino-1-hydroxyethyl)-6-hydroxy-1,4-benzoxazine-3(4H)-one derivatives as potent β2-adrenoceptor agonists
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A series of β2-adrenoceptor agonists with an 8-(2-amino-1-hydroxyethyl)-6-hydroxy-1,4-benzoxazine-3(4H)-one moiety is presented. The stimulatory effects of the compounds on human β2-adrenoceptor and β1-adrenoceptor were characterized by a cell-based assay. Their smooth muscle relaxant activities were tested on isolated guinea pig trachea. Most of the compounds were found to be potent and selective agonists of the β2-adrenoceptor. One of the compounds, (R)-18c, possessed a strong β2-adrenoceptor agonistic effect with an EC50 value of 24 pM. It produced a full and potent airway smooth muscle relaxant effect same as olodaterol. Its onset of action was 3.5 min and its duration of action was more than 12 h in an in vitro guinea pig trachea model of bronchodilation. These results suggest that (R)-18c is a potential candidate for long-acting β2-AR agonists.
- Yi, Ce,Xing, Gang,Wang, Siqi,Li, Xiaoran,Liu, Yichuang,Li, Jinyan,Lin, Bin,Woo, Anthony Yiu-Ho,Zhang, Yuyang,Pan, Li,Cheng, Maosheng
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- Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
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Herein, a Grubbs-catalyzed route for the synthesis of nitriles via the aerobic oxidation of primary amines is reported. This reaction accommodates a variety of substrates, including simple primary amines, sterically hindered β,β-disubstituted amines, allylamine, benzylamines, and α-amino esters. Reaction compatibility with various functionalities is also noted, particularly with alkenes, alkynes, halogens, esters, silyl ethers, and free hydroxyl groups. The nitriles were also synthesized via the oxidation of imines generated from aldehydes and NH4OAc in situ. (Figure presented.).
- Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
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supporting information
p. 3583 - 3588
(2020/08/05)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
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- One-pot synthesis of aldoximes from alkenes: Via Rh-catalysed hydroformylation in an aqueous solvent system
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Aldoxime synthesis directly starting from alkenes was successfully achieved through the combination of hydroformylation and subsequent condensation of the aldehyde intermediate with aqueous hydroxylamine in a one-pot process. The metal complex Rh(acac)(CO)2 and the water-soluble ligand sulfoxantphos were used as the catalyst system, providing high regioselectivities in the initial hydroformylation. A mixture of water and 1-butanol was used as an environmentally benign solvent system, ensuring sufficient contact of the aqueous catalyst phase and the organic substrate phase. The reaction conditions were systematically optimised by Design of Experiments (DoE) using 1-octene as a model substrate. A yield of 85% of the desired linear, terminal aldoxime ((E/Z)-nonanal oxime) at 95% regioselectivity was achieved. Other terminal alkenes were also converted successfully under the optimised conditions to the corresponding linear aldoximes, including renewable substrates. Differences of the reaction rate have been investigated by recording the gas consumption, whereby turnover frequencies (TOFs) >2000 h-1 were observed for 4-vinylcyclohexene and styrene, respectively. The high potential of aldoximes as platform intermediates was shown by their subsequent transformation into the corresponding linear nitriles using aldoxime dehydratases as biocatalysts. The overall reaction sequence thus allows for a straightforward synthesis of linear nitriles from alkenes with water being the only by-product, which formally represents an anti-Markovnikov hydrocyanation of readily available 1-alkenes.
- Gr?ger, H.,Guntermann, A.,Hinzmann, A.,Jolmes, T.,Panke, D.,Plass, C.,R?sler, J.,Seidensticker, T.,Terhorst, M.,Vogt, D.,Vorholt, A. J.
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p. 7974 - 7982
(2020/11/30)
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- Visible- And UV-Light-Induced Decarboxylative Radical Reactions of Benzoic Acids Using Organic Photoredox Catalysts
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Photoinduced decarboxylative radical reactions of benzoic acids with electron-deficient alkenes, diborane, and acetonitrile under organic photoredox catalysis conditions and mild heating afforded adducts, arylboronate esters, and the reduction product, respectively. The reaction is thought to involve single-electron transfer promoted the generation of aryl radicals via decarboxylation. A diverse range of benzoic acids were found to be suitable substrates for this photoreaction. Only our two-molecule organic photoredox system can work well for the direct photoinduced decarboxylation of benzoic acids.
- Kubosaki, Suzuka,Takeuchi, Haruka,Iwata, Yutaka,Tanaka, Yosuke,Osaka, Kazuyuki,Yamawaki, Mugen,Morita, Toshio,Yoshimi, Yasuharu
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p. 5362 - 5369
(2020/05/19)
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- Efficient Co-Catalyzed Double Hydroboration of Nitriles: Application to One-Pot Conversion of Nitriles to Aldimines
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The commercially available and bench-stable Co(acac)2/dpephos system is employed as a precatalyst for selective and efficient room temperature hydroboration of organic nitriles with HBPin to produce a series of N,N-diborylamines [RN(BPin)2], which react in situ with aldehydes to give aldimines. Formation of aldimines from N,N-diborylamines does not require a dehydrating agent, is applicable to a wide range of N,N-diborylamine and aldehyde substrates and is highly chemoselective, being unaffected by various common functional groups, such as alkenes, alkynes, secondary amines, ketones, esters, amides, carboxylic acids, pyridines, nitriles, and nitro compounds. The overall transformation represents a synthetically valuable approach to aldimines from nitriles and can be performed in a sequential one-pot manner, tolerating ester, lactone, carboxamide and unactivated alkene functionalities.
- Gudun, Kristina A.,Slamova, Ainur,Hayrapetyan, Davit,Khalimon, Andrey Y.
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supporting information
p. 4963 - 4968
(2020/04/17)
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- Nickel-Catalyzed Markovnikov Transfer Hydrocyanation in the Absence of Lewis Acid
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Hydrocyanation in the absence of toxic HCN gas is highly desirable. Addressing that challenge, transition-metal-catalyzed transfer hydrocyanation using safe HCN precursors has been developed, but these reagents generally require a Lewis acid for activation, and the control of regioselectivity often remains problematic. In this Letter, a Ni-catalyzed highly Markovnikov-selective transfer hydrocyanation that operates in the absence of any Lewis acid is reported. The readily prepared pro-aromatic 1-isopropylcyclohexa-2,5-diene-1-carbonitrile is used as the HCN source, and the reaction shows a broad substrate scope and high functional group tolerance. Terminal styrene derivatives, dienes, and internal alkynes are converted with good to excellent selectivities. Mechanistic studies provide insights into the origin of the regioselectivity.
- Frye, Nils L.,Bhunia, Anup,Studer, Armido
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supporting information
p. 4456 - 4460
(2020/06/03)
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- Overcoming Selectivity Issues in Reversible Catalysis: A Transfer Hydrocyanation Exhibiting High Kinetic Control
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Reversible catalytic reactions operate under thermodynamic control, and thus, establishing a selective catalytic system poses a considerable challenge. Herein, we report a reversible transfer hydrocyanation protocol that exhibits high selectivity for the thermodynamically less favorable branched isomer. Selectivity is achieved by exploiting the lower barrier for C-CN oxidative addition and reductive elimination at benzylic positions in the absence of a cocatalytic Lewis acid. Through the design of a novel type of HCN donor, a practical, branched-selective, HCN-free transfer hydrocyanation was realized. The synthetically useful resolution of a mixture of branched and linear nitrile isomers was also demonstrated to underline the value of reversible and selective transfer reactions. In a broader context, this work demonstrates that high kinetic selectivity can be achieved in reversible transfer reactions, thus opening new horizons for their synthetic applications.
- Bhawal, Benjamin N.,Ehinger, Christian,Morandi, Bill,Reisenbauer, Julia C.
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supporting information
p. 10914 - 10920
(2020/07/13)
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- Transformations of Aryl Ketones via Ligand-Promoted C?C Bond Activation
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The coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is a core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in an analogous manner via carbon–carbon bond activation could greatly expand the toolbox for the synthesis of aryl compounds due to the abundance of aryl ketones. An exploratory study of this approach is typically based on carbon–carbon cleavage triggered by ring-strain release and chelation assistance, and the products are also limited to a specific structural motif. Here we report a ligand-promoted β-carbon elimination strategy to activate the carbon–carbon bonds, which results in a range of transformations of aryl ketones, leading to useful aryl borates, and also to biaryls, aryl nitriles, and aryl alkenes. The use of a pyridine-oxazoline ligand is crucial for this catalytic transformation. A gram-scale borylation reaction of an aryl ketone via a simple one-pot operation is reported. The potential utility of this strategy is also demonstrated by the late-stage diversification of drug molecules probenecid, adapalene, and desoxyestrone, the fragrance tonalid as well as the natural product apocynin.
- Dai, Hui-Xiong,Li, Hanyuan,Li, Ling-Jun,Liu, Qi-Sheng,Ma, Biao,Wang, Mei-Ling,Wang, Xing,Wang, Zhen-Yu,Xu, Hui
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supporting information
p. 14388 - 14393
(2020/07/06)
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- Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
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Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.
- Dong, Yanan,Li, Yuehui,Yang, Peiju,Zhao, Shizhen
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- A State-of-the-Art Heterogeneous Catalyst for Efficient and General Nitrile Hydrogenation
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Cobalt-doped hybrid materials consisting of metal oxides and carbon derived from chitin were prepared, characterized and tested for industrially relevant nitrile hydrogenations. The optimal catalyst supported onto MgO showed, after pyrolysis at 700 °C, magnesium oxide nanocubes decorated with carbon-enveloped Co nanoparticles. This special structure allows for the selective hydrogenation of diverse and demanding nitriles to the corresponding primary amines under mild conditions (e.g. 70 °C, 20 bar H2). The advantage of this novel catalytic material is showcased for industrially important substrates, including adipodinitrile, picolinonitrile, and fatty acid nitriles. Notably, the developed system outperformed all other tested commercial catalysts, for example, Raney Nickel and even noble-metal-based systems in these transformations.
- Formenti, Dario,Mocci, Rita,Atia, Hanan,Dastgir, Sarim,Anwar, Muhammad,Bachmann, Stephan,Scalone, Michelangelo,Junge, Kathrin,Beller, Matthias
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supporting information
p. 15589 - 15595
(2020/10/02)
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- OXIDATIVE CONVERSION OF ALIPHATIC ALDEHYDES TO NITRILES USING OXOAMMONIUM SALT
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The present invention relates to an oxidative transformation method of aliphatic benzaldehydes to nitriles using NH_4OAc through oxoammonium salts. By using stoichiometric amounts of oxoammonium salts to establish optimal reaction conditions associated with the oxidative conversion of aliphatic benzaldehydes to nitriles, high yields of nitrile can be selectively obtained, and the oxoammonium salts used can be oxidized and reused in a simple method.COPYRIGHT KIPO 2020
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Paragraph 0055-0063; 0136-0142
(2019/12/10)
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- Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat
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A novel approach to convert aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8 has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.
- Chen, Han,Sun, Sijia,Xi, Haoying,Hu, Kaifang,Zhang, Ning,Qu, Jingping,Zhou, Yuhan
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supporting information
p. 1434 - 1436
(2019/05/01)
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- Sulfuryl Fluoride Mediated Conversion of Aldehydes to Nitriles
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Aliphatic, aromatic, and heteroaromatic aldehydes were readily converted to corresponding nitriles in a one-pot reaction sequence with hydroxylamine and sulfuryl fluoride. The reaction proceeds at room temperature, does not require metal catalysts and special precautions, and produces nitriles in excellent yields. It is compatible with a variety of functional groups, can be performed in aqueous and organic solvents, and is readily scalable to multigram quantities. Mild conditions and high selectivity of the reaction enabled the construction of polyfunctional probes containing nitrile, alkyne, azide, and fluorosulfate groups for further orthogonal derivatization.
- Gurjar, Jitendra,Bater, Jorick,Fokin, Valery V.
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supporting information
p. 1906 - 1909
(2019/01/24)
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- SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
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A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO 2 F 2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho -, meta - and para -nitrile groups was also described in aqueous methanol by using inorganic base Na 2 CO 3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.
- Ding, Chengrong,Mei, Guangyao,Wang, Haibo,Zhang, Guofu,Zhao, Yiyong
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p. 1484 - 1488
(2019/07/15)
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- Celite-Polyaniline supported palladium catalyst for chemoselective hydrogenation reactions
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Polyaniline coated on particles of celite is used as support to load palladium catalyst. This heterogenized Celite?PANI?Pd system, is used as an efficient catalyst for chemoselective hydrogenation reactions. The catalyst is characterized by usual spectral, analytical techniques and studied for hydrogenation reactions at ambient conditions. The mild reaction conditions allow the control over the reactions and excellent selectivity is achieved in number of conversions. Hydrogenation of a carbon–carbon double bond was favored over other polar π-bond systems, while labile functional groups such as benzyl ether, benzyl esters, cyano, nitro and halogen remained unaffected. Primary amines were converted to N,N-dimethyl amines with formaldehyde, the double bond of coumarin was selectively hydrogenated without opening of the lactone functionality.
- Patel, Heta A.,Rawat, Maitreyee,Patel, Arun L.,Bedekar, Ashutosh V.
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- Electrochemical Hydrogenation with Gaseous Ammonia
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As a carbon-free and sustainable fuel, ammonia serves as high-energy-density hydrogen-storage material. It is important to develop new reactions able to utilize ammonia as a hydrogen source directly. Herein, we report an electrochemical hydrogenation of alkenes, alkynes, and ketones using ammonia as the hydrogen source and carbon electrodes. A variety of heterocycles and functional groups, including for example sulfide, benzyl, benzyl carbamate, and allyl carbamate were well tolerated. Fast stepwise electron transfer and proton transfer processes were proposed to account for the transformation.
- Li, Jin,He, Lingfeng,Liu, Xu,Cheng, Xu,Li, Guigen
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supporting information
p. 1759 - 1763
(2019/01/16)
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- Chemoselective transfer hydrogenation of Α,Β-unsaturated carbonyls catalyzed by a reusable supported Pd nanoparticles on biomass-derived carbon
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We herein report highly chemoselective transfer hydrogenation of α,β-unsaturated carbonyl compounds to saturated carbonyls with formic acid as a hydrogen donor over a stable and recyclable heterogeneous Pd nanoparticles (NPs) on N,O-dual doped hierarchical porous biomass-derived carbon. The synergistic effect between Pd NPs and incorporated heteroatoms on carbon plays a critical role on promoting the reaction efficiency. A series of α,β-aromatic and aliphatic unsaturated carbonyl compounds was selectively reduced to their corresponding saturated carbonyls in up to 97% isolated yields with good tolerance of various functional groups. In addition, the catalyst can be successively reused for at least 6 times without significant loss in reaction efficiency.
- Song, Tao,Duan, Yanan,Yang, Yong
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- Chemoselective Hydrogenation of α,β-Unsaturated Carbonyls Catalyzed by Biomass-Derived Cobalt Nanoparticles in Water
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Herein, we report highly chemoselective hydrogenation of α,β-unsaturated carbonyls to saturated carbonyls catalyzed by cobalt nanoparticles supported on the biomass-derived carbon from bamboo shoots with molecular hydrogen in water, which is the first prototype using a heterogeneous non-noble metal catalyst for such organic transformation as far as we know. The optimal cobalt nanocatalyst, CoOx@NC-800, manifested remarkable activity and selectivity for hydrogenation of C=C in α,β-unsaturated carbonyls under mild conditions. A broad set of α,β-aromatic and aliphatic unsaturated carbonyls were selectively reduced to their corresponding saturated carbonyls in up to 99 % yields with good tolerance of various functional groups. Meanwhile, a new straightforward one-pot cascade synthesis of saturated carbonyls was realized with high activity and selectivity via the cross-aldol condensation of ketones with aldehydes followed by selective hydrogenation. More importantly, this one-pot strategy is applicable for the expedient synthesis of Loureirin A, a versatile bioactive and medicinal molecule, from readily available starting materials, further highlighting the practical utility of the catalyst. In addition, the catalyst can be easily separated for successive reuses without significant loss in both activity and selectivity.
- Song, Tao,Ma, Zhiming,Yang, Yong
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p. 1313 - 1319
(2019/01/25)
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- Identification of an Active NiCu Catalyst for Nitrile Synthesis from Alcohol
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Development of heterogeneous catalysts for alcohol transformation into nitriles under oxidant-free conditions is a challenge. Considering the C-H activation on α-carbon of primary alcohols is the rate-determining step, decreasing the activation energy of C-H activation is critical in order to enhance the catalytic activity. Several NiM/Al2O3 bimetallic catalysts were synthesized and scrutinized in catalytic transformation of 1-butanol to butyronitrile. Ni-Cu was identified as a suitable combination with the optimized Ni0.5Cu0.5/Al2O3 catalyst exhibiting 10 times higher turnover frequency than Ni/Al2O3 catalyst. X-ray absorption spectroscopy (XAS) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) revealed that the NiCu particles in the catalyst exist in the form of homogeneous alloys with an average size of 8.3 nm, providing an experimental foundation to build up a catalyst model for further density functional theory (DFT) calculations. Calculations were done over a series of NiM catalysts, and the experimentally observed activity trend could be rationalized by the Br?nsted-Evans-Polanyi (BEP) principle, i.e., catalysts that afford reduced reaction energy also feature lower activation barriers. The calculated activation energy (Ea) for C-H activation with coadsorbed NH3 dropped from 63.4 kJ/mol on pure Ni catalyst to 49.9 kJ/mol on the most active NiCu-2 site in NiCu bimetallic catalyst, in good agreement with the experimentally measured activation energy values. The Ni0.5Cu0.5/Al2O3 catalyst was further employed to convert 11 primary alcohols into nitriles with high to near-quantitative yields, at a Ni loading 10 times less than that of the conventional Ni/Al2O3 catalyst.
- Wang, Yunzhu,Furukawa, Shinya,Yan, Ning
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p. 6681 - 6691
(2019/07/12)
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- Oxidant free conversion of alcohols to nitriles over Ni-based catalysts
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Organic nitriles are significant and versatile industrial feedstocks, but their conventional synthetic protocols require hazardous starting materials and/or harsh reaction conditions posing environmental and health risks. Herein, we established a Ni-based catalytic system to convert primary alcohols to nitriles with ammonia gas as the sole nitrogen source under oxidant-free conditions at merely 190-230 °C. Based on isotope labelling experiments, in situ DRIFTS and control experiments, the reaction pathway was identified to follow a dehydrogenation-imination-dehydrogenation sequence, with α-carbon C-H bond breakage as the rate determining step. Ni is superior to all noble metal catalysts tested, due to its excellent dehydrogenation ability that is not inhibited by NH3. The support plays an auxiliary role, promoting the reaction between aldehyde and ammonia to form imine as a critical intermediate. Ni/Al2O3 catalyst prepared via a deposition-precipitation method, featuring both excellent dispersion of metallic Ni and suitable acid sites, enabled alcohol transformation into nitrile under unprecedented low temperature. Various alcohols were converted into their corresponding nitriles in high conversions and yields (both up to 99%), while the catalyst kept 90% of its original activity after 48 hours in the stability test, highlighting the wide applicability and the robustness of the catalytic system.
- Wang, Yunzhu,Furukawa, Shinya,Zhang, Zhang,Torrente-Murciano, Laura,Khan, Saif A.,Yan, Ning
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- Titanium(III)-Catalyzed Reductive Decyanation of Geminal Dinitriles by a Non-Free-Radical Mechanism
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A titanium-catalyzed mono-decyanation of geminal dinitriles is reported. The reaction proceeds under mild conditions, tolerates numerous functional groups, and can be applied to quaternary malononitriles. A corresponding desulfonylation is demonstrated as well. Mechanistic experiments support a catalyst-controlled cleavage without the formation of free radicals, which is in sharp contrast to traditional stoichiometric radical decyanations. The involvement of two TiIII species in the C?C cleavage is proposed, and the beneficial role of added ZnCl2 and 2,4,6-collidine hydrochloride is investigated.
- Weweler, Jens,Younas, Sara L.,Streuff, Jan
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supporting information
p. 17700 - 17703
(2019/11/13)
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- Easy Ruthenium-Catalysed Oxidation of Primary Amines to Nitriles under Oxidant-Free Conditions
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A dehydrogenation of primary amine to give the corresponding nitrile under oxidant- and base-free conditions catalysed by simple [Ru(p-cym)Cl2]2 with no extra ligand is reported. The system is highly selective for alkyl amines, whereas benzylamine derivatives gave the nitrile product together with the imine in a ratio ranging from 14:1 to 4:1 depending on the substrate. Preliminary mechanistic investigations have been performed to identify the key factors that govern the selectivity.
- Achard, Thierry,Egly, Julien,Sigrist, Michel,Maisse-Fran?ois, Aline,Bellemin-Laponnaz, Stéphane
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supporting information
p. 13271 - 13274
(2019/10/21)
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- Method for preparing nitrile by reacting acetone cyanohydrin with haloalkane
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The invention provides a method for preparing nitrile by reacting acetone cyanohydrin with haloalkane. According to the invention, by using acetone cyanohydrin as a cyaniding reagent, the problems, such as long reaction time, low yield, strict reaction conditions and the like enchanted in an existing preparation method in which highly toxic sodium cyanide or potassium cyanide or expensive trimethylsilyl cyanide is used as a cyanogen source, are solved. The method comprises the following steps: dissolving acetone cyanohydrin in a mixed solvent of a high boiling point dipolar aprotic solvent anda low boiling point aprotic solvent, adding a catalyst lithium hydroxide, stirring at 25-50 DEG C for one hour and then adding a haloalkane for continuous reaction for 2-3 hours; next, adding saturated saline water for washing twice, separating out an organic layer, and boiling off the solvent after drying, thereby obtaining a nitrile compound. The method for preparing a nitrile compound disclosed in the invention is characterized by low reaction toxicity, simple process, easy of operation, low production cost, and a yield of more than 95%.
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Paragraph 0043-0049; 0051-0057; 0059
(2019/08/20)
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- Thiocyanate radical mediated dehydration of aldoximes with visible light and air
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We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol for a wide range of nitriles.
- Ban, Yong-Liang,Dai, Jian-Ling,Jin, Xiao-Ling,Zhang, Qing-Bao,Liu, Qiang
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supporting information
p. 9701 - 9704
(2019/08/15)
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- Electrocarboxylation of halobenzonitriles: An environmentally friendly synthesis of phthalate derivatives
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This manuscript presents an efficient approach for producing high valuable compounds using CO2 as building block. The methodology employed is based on electrochemical techniques, which allow performing eco-friendly chemistry solutions and maintaining the aim of offering a potential long-term strategy for reducing the CO2 emissions in the atmosphere, while obtaining useful compounds, such as aromatic acids and phthalate derivatives. This work describes the electrochemical reduction behavior of 4-halobenzonitrile compounds using Glassy Carbon and Silver as cathodes under inert and carbon dioxide atmosphere. Controlled potential electrolysis of 4-halobenzonitriles under CO2 allows obtaining, in very good yields, the corresponding mono- and di-carboxylated organic compounds in CO2-saturated solutions of dimethylformamide containing 0.1 M of tetrabutylammonium tetrafluoroborate. Electro-catalytic effects are seen when Ag is used a cathode, which give very high yields, especially as regards di-carboxylated products. The methodology offers a new “green” route for the synthesis of different phthalate derivatives, which can be potentially used for making plastic polymers in a more environmentally friendly way.
- Reche, Irene,Mena, Silvia,Gallardo, Iluminada,Guirado, Gonzalo
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- Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
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The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
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supporting information
p. 266 - 273
(2018/01/12)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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Paragraph 0153; 0154; 0155; 0156; 0157
(2018/05/07)
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- A strategy for generating aryl radicals from arylborates through organic photoredox catalysis: Photo-Meerwein type arylation of electron-deficient alkenes
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Photoinduced reactions of arylboronic acids with electron deficient alkenes under mild organic photoredox catalysis conditions lead to the formation of Meerwein arylation type adducts via the generation of aryl radicals.
- Iwata,Tanaka,Kubosaki,Morita,Yoshimi
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supporting information
p. 1257 - 1260
(2018/02/09)
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- Surprising and Highly Efficient Use of Methylmagnesium Chloride as a Non-Nucleophilic Base in the Deprotonation and Alkylation of sp3 Centres Adjacent to Nitriles
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Methylmagnesium chloride (MeMgCl) is a key reagent in research and industry typically as a nucleophile. In this article we develop the use of MeMgCl as a non-nucleophilic base in conjunction with catalytic amounts of an amine mediator. Specifically, we use the base to deprotonate α to a variety of nitriles in alkylation reactions, applying it to the synthesis of a wide variety of tertiary and quaternary nitriles, including examples where we successively and successfully added three different substituents on the carbon α to the nitrile. This method is generally applicable, high yielding and much greener than existing methods, and it has considerable advantages for industrial application.
- Gbadebo, Omolola,Smith, Dennis,Harnett, Ger,Donegan, Gregory,O'Leary, Patrick
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p. 7037 - 7045
(2019/01/04)
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- Boosting Hydrogen Production by Anodic Oxidation of Primary Amines over a NiSe Nanorod Electrode
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For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts the cathodic hydrogen evolution reaction (HER). Therefore, developing an alternative anodic reaction with accelerating kinetics to produce value-added chemicals, especially coupled with HER, is of great importance. Now, a thermodynamically more favorable primary amine (?CH2?NH2) electrooxidation catalyzed by NiSe nanorod arrays in water is reported to replace OER for enhancing HER. The increased H2 production can be obtained at cathode; meanwhile, a variety of aromatic and aliphatic primary amines are selectively electrooxidized to nitriles with good yields at the anode. Mechanistic investigations suggest that NiII/NiIII may serve as the redox active species for the primary amines transformation. Hydrophobic nitrile products can readily escape from aqueous electrolyte/electrode interface, avoiding the deactivation of the catalyst and thus contributing to continuous gram-scale synthesis.
- Chong, Xiaodan,Huang, Yi,Liang, Yu,Liu, Cuibo,Zhang, Bin
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supporting information
p. 13163 - 13166
(2018/09/21)
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- Aerobic Oxidative Dehydrogenation of Amines Catalyzed by a Recoverable Ruthenium Catalyst under Mild Reaction Conditions
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A highly active catalyst based on perruthenate ions supported inside the channels of periodic mesoporous organosilica with a bridged imidazolium ionic liquid framework (Ru@PMO-IL) was developed. The material was found to be an efficient, durable, and recoverable catalyst for the oxidative dehydrogenation of various types of amines such as benzylic, aliphatic, and cyclic aliphatic amines under mild reaction conditions. The products were obtained in excellent yields with excellent selectivities.
- Karimi, Babak,Yari, Omolbanin,Khorasani, Mojtaba,Vali, Hojatollah,Mansouri, Fariborz
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p. 1783 - 1787
(2018/01/27)
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- Synthesis of Nitriles from Primary Amides or Aldoximes under Conditions of a Catalytic Swern Oxidation
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The preparation of nitriles from primary amides or aldoximes was achieved by using oxalyl chloride with a catalytic amount of dimethyl sulfoxide in the presence of Et3N. The reactions were complete within 1 h after addition at room temperature. A diverse range of cyano compounds were obtained in good to excellent yields, including aromatic, heteroaromatic, cyclic, and acyclic aliphatic species.
- Ding, Rui,Liu, Yongguo,Han, Mengru,Jiao, Wenyi,Li, Jiaqi,Tian, Hongyu,Sun, Baoguo
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p. 12939 - 12944
(2018/10/20)
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- Pd/Mn Bimetallic Relay Catalysis for Aerobic Aldoxime Dehydration to Nitriles
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A Pd/Mn bimetal system was found to be an effective catalyst for dehydration of aldoximes to the useful nitriles under mild aerobic conditions. Different to the known metal-catalyzed aldoxime dehydration reactions, this reaction very possibly proceeded via an alternative mechanism of Pd/Mn bimetal relay catalysis involving a Mn-catalyzed aerobic oxidation of aldoximes to nitrile oxides by air and a Pd-catalyzed oxygen transfer from the nitrile oxides to the solvent acetonitrile. This method tolerates a variety of substrates including sterically bulky ones and also the natural product derivative. (Figure presented.).
- Zhang, Dongliang,Huang, Yaping,Zhang, Erlei,Yi, Rong,Chen, Chao,Yu, Lei,Xu, Qing
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supporting information
p. 784 - 790
(2018/01/04)
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- Cooperative Palladium/Lewis Acid-Catalyzed Transfer Hydrocyanation of Alkenes and Alkynes Using 1-Methylcyclohexa-2,5-diene-1-carbonitrile
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Catalytic transfer hydrocyanation represents a clean and safe alternative to hydrocyanation processes using toxic HCN gas. Such reactions provide access to pharmaceutically important nitrile derivatives starting with alkenes and alkynes. Herein, an efficient and practical cooperative palladium/Lewis acid-catalyzed transfer hydrocyanation of alkenes and alkynes is presented using 1-methylcyclohexa-2,5-diene-1-carbonitrile as a benign and readily available HCN source. A large set of nitrile derivatives (>50 examples) are prepared from both aliphatic and aromatic alkenes with good to excellent anti-Markovnikov selectivity. A range of aliphatic alkenes engage in selective hydrocyanation to provide the corresponding nitriles. The introduced method is useful for chain walking hydrocyanation of internal alkenes to afford terminal nitriles in good regioselectivities. This protocol is also applicable to late-stage modification of bioactive molecules.
- Bhunia, Anup,Bergander, Klaus,Studer, Armido
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supporting information
p. 16353 - 16359
(2018/11/25)
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