- Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
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A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.
- Iizumi, Keiichiro,Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
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supporting information
p. 1555 - 1559
(2020/11/10)
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- Nickel-Catalyzed Transformation of Alkene-Tethered Oxime Ethers to Nitriles by a Traceless Directing Group Strategy
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Nickel-catalyzed transformation of alkene-tethered oxime ethers to nitriles using a traceless directing group strategy has been developed. A series of alkene-tethered oxime ethers derived from benzaldehyde and cinnamyl aldehyde derivatives were converted into the corresponding benzonitriles and cinnamonitriles in 46-98% yields using the nickel catalyst system. Control experiments showed that the alkene group tethered to an oxygen atom on the oximes via one methylene unit plays a key role as a traceless directing group during the catalysis.
- Takahashi, Yoshiyuki,Tsuji, Hiroaki,Kawatsura, Motoi
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p. 2654 - 2665
(2020/02/04)
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- Method for converting aromatic aldehyde into aromatic nitrile by using sulfur powder promoted inorganic ammonium as nitrogen source (by machine translation)
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The invention discloses a method for converting aromatic aldehyde into aromatic nitrile. The method is conversion of high yield of aromatic aldehyde one-pot reaction of sulfur powder promoted inorganic ammonium as a nitrogen source into aromatic nitrile. The method has the advantages of no need of metal participation, no need of strong oxide, compatibility of reaction to air, easiness in amplification to a gram scale and the like, and overcomes the problems of harsh reaction conditions, complex operation, low functional group compatibility and the like in the prior art. (by machine translation)
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Paragraph 0072; 0073
(2020/09/12)
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- A carboxamide is the cyanogen source of aromatic nitrile to the preparation method of the (by machine translation)
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The invention discloses a method for preparing aromatic nitrile, is under the action of the nickel catalyst, in order to carboxamide is the cyanogen source, and with various substituents haloarene coupled reactions, preparing aromatic nitrile. The reaction temperature is 100 - 160 °C, the reaction time is 6 - 24 hours. It overcomes the traditional aromatic nitrile of the synthesis method operation of complex steps, requires the use of a toxic, more expensive, functionalization of the cyanogen source as the reaction raw material and the like. Compared with the traditional method, this method is simple to use cheap, green non-toxic of the formamide is cyano sources; without the need of external dehydrating agent, formamide in the nickel catalyst of the catalytic dehydration at the same time, with a nickel catalyst in coordination with the halogenated aromatic hydrocyanation, more economic, high-efficiency, environmental protection; at the same time the method exhibits good substrate universality, to air, moisture, light are not sensitive, high yield, product separation and purification is simple, with wide application. (by machine translation)
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Paragraph 0015; 0016; 0017; 0018-0024; 0116; 0117-0120
(2019/05/08)
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- Ni-Mediated Generation of "cN" Unit from Formamide and Its Catalysis in the Cyanation Reactions
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The in situ generation of a "cyano" unit from readily available organic precursors is of high interest in synthetic chemistry. Herein, we report the first example of Ni-mediated dehydration of formamide to form "CN" and its subsequent catalytic applications in the hydrocyanation of alkynes and cyanation of aryl halides. Formamide can serve as a convenient source for the nitrile unit, in that it releases water as the only byproduct.
- Yang, Luo,Liu, Yu-Ting,Park, Yoonsu,Park, Sung-Woo,Chang, Sukbok
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p. 3360 - 3365
(2019/03/26)
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- Synthesis method of benzonitrile compounds
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The invention provides a preparation method of benzonitrile compounds. The preparation method comprises the steps: carrying out a reaction in an organic solvent at 0-50 DEG C for 4-12h under the action of an oxidant by taking phenylacetylene as shown in the formula (I) and a derivative of phenylacetylene as raw materials and nitrite as a nitrogen source, and separating and purifying the obtained reaction liquid to prepare the benzonitrile compound as shown in the formula (II); and the amount-of-substance ratio of the nitrogen source to phenylacetylene as shown in the formula (I) and the derivative of phenylacetylene is (1-3):1. The preparation method is simple and available in raw material, mild in reaction condition, good in functional group tolerance, simple in operation and environment-friendly so as to be a novel method for synthesizing benzonitrile containing various substituent groups.
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Paragraph 0080; 0081; 0082
(2018/04/02)
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- Decarbonylative Cyanation of Amides by Palladium Catalysis
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Transition-metal-catalyzed cyanation of aryl halides is a process of significant importance in the preparation pharmaceuticals, organic materials and agrochemicals. Here, we demonstrate a palladium-catalyzed decarbonylative cyanation of amides by highly selective carbon-nitrogen bond cleavage for the synthesis of a wide range of aryl nitriles. The utility of this technology is demonstrated by the synthesis of isotopically labeled aryl nitriles and orthogonal cross-coupling reactions of bench-stable amides to establish cross-coupling synthons with opposite polarity.
- Shi, Shicheng,Szostak, Michal
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supporting information
p. 3095 - 3098
(2017/06/23)
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- Aryl Nitriles from Alkynes Using tert -Butyl Nitrite: Metal-Free Approach to C≡C Bond Cleavage
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Alkyne C≡C bond breaking, outside of alkyne metathesis, remains an underdeveloped area in reaction discovery. Recently, nitrogenation has been reported to allow nitrile formation from alkynes. A new protocol for the metal-free C≡C bond cleavage of terminal alkynes to produce nitriles is reported. This method provides an opportunity to synthesize a vast range of nitriles containing aryl, heteroaryl, and natural product derivatives (38 examples). In addition, the potential of tBuONO to act as a powerful nitrogenating agent for terminal aryl alkynes is demonstrated. (Figure Presented).
- Dutta, Uttam,Lupton, David W.,Maiti, Debabrata
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supporting information
p. 860 - 863
(2016/03/01)
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- Aerobic Copper-Promoted Radical-Type Cleavage of Coordinated Cyanide Anion: Nitrogen Transfer to Aldehydes to Form Nitriles
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We have disclosed for the first time the copper-promoted C≡N triple bond cleavage of coordinated cyanide anion under a dioxygen atmosphere, which enables a nitrogen transfer to various aldehydes. Mechanistic study of this unprecedented transformation suggests that the single electron-transfer process could be involved in the overall course. This protocol provides a new cleavage pattern for the cyanide ion and would eventually lead to a more useful synthetic pathway to nitriles from aldehydes.
- Wu, Qian,Luo, Yi,Lei, Aiwen,You, Jingsong
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supporting information
p. 2885 - 2888
(2016/03/19)
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- Design, Conformation, and Crystallography of 2-Naphthyl Phenyl Ethers as Potent Anti-HIV Agents
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Catechol diethers that incorporate a 7-cyano-2-naphthyl substituent are reported as non-nucleoside inhibitors of HIV-1 reverse transcriptase (NNRTIs). Many of the compounds have 1-10 nM potencies toward wild-type HIV-1. An interesting conformational effect allows two unique conformers for the naphthyl group in complexes with HIV-RT. X-ray crystal structures for 4a and 4f illustrate the alternatives.
- Lee, Won-Gil,Chan, Albert H.,Spasov, Krasimir A.,Anderson, Karen S.,Jorgensen, William L.
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supporting information
p. 1156 - 1160
(2016/12/16)
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- One-pot synthesis of amidoxime via Pd-catalyzed cyanation and amidoximation
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A novel "one-pot" reaction was developed for the synthesis of aryl or heteroaryl-substituted amidoxime compounds containing various functional groups. Fluorescence titration experiments coupled with theoretical analysis revealed that the steric hindrance and electronic effects of substituents influence the binding ability of the amidoxime compounds to uranyl ions. This journal is
- Yang, Chu-Ting,Han, Jun,Liu, Jun,Gu, Mei,Li, Yi,Wen, Jun,Yu, Hai-Zhu,Hu, Sheng,Wang, Xiaolin
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supporting information
p. 2541 - 2545
(2015/04/14)
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- Ethyl cyanoacetate: A new cyanating agent for the palladium-catalyzed cyanation of aryl halides
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A new Pd-catalyzed cyanation reaction has been discovered using ethyl cyanoacetate as the cyanating reagent. A variety of electron-rich and electron-deficient aryl halides were efficiently converted into their corresponding nitriles in good to excellent yields.
- Zheng, Shuyan,Yu, Chunhui,Shen, Zhengwu
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supporting information; experimental part
p. 3644 - 3647
(2012/08/28)
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- Efficient cyanation of aryl bromides with K4[Fe(CN)6] catalyzed by a palladium-indolylphosphine complex
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This study describes a general palladium-catalyzed cyanation of aryl bromides using K4[Fe(CN)6] as the cyanide surrogate. The reactions can be successfully conducted under mild reaction conditions (at 50 °C) in mixed solvents (water/MeCN = 1:1) without any surfactant additives, and afford the desired aryl nitriles in good-to-excellent yields. Particularly noteworthy is that this system allows the mildest reaction temperature reported so far for palladium-catalyzed cyanation of aryl bromides with K 4[Fe(CN)6] source in general. Common functional groups, including keto, aldehyde, free amine, and heterocyclic substrates are compatible under this system. Interestingly, the phosphine ligands bearing -PCy 2 moiety, which usually show excellent activity in aryl halide couplings, are found less effective than the corresponding ligands with -PPh2 group.
- Yeung, Pui Yee,Tsang, Chun Pui,Kwong, Fuk Yee
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experimental part
p. 7038 - 7041
(2012/01/05)
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- A novel and convenient synthesis of benzonitriles: Electrophilic cyanation of aryl and heteroaryl bromides
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N-Cyano-N-phenyl-p-methylbenzenesulfonamide has been used as a more benign electrophilic cyanation reagent for the synthesis of various benzonitriles from (hetero)aryl bromides via formation of Grignard reagents. Electronically different and sterically demanding aryl bromides including functionalized substrates and heteroaryl bromides are successfully cyanated in good to excellent yields. The efficiency of the present methodology is shown by the expeditious syntheses of interesting pharmaceutical intermediates. Notably, chemoselective monocyanation of dibromoarenes is also achieved. Copyright
- Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 4217 - 4222
(2011/05/06)
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- A convenient synthesis of benzonitriles via electrophilic cyanation with N-cyanobenzimidazole
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(Chemical Equation Presented) Couplings: N-Cyanobenzimidazole has been used in the synthesis of aryl- and heteroarylnitriles from the corresponding Grignard reagents (see scheme). This electrophilic cyanation is further extended to the synthesis of 2-cyano1,1'-biaryls through a domino Grignard-coupling/ cyanation strategy.
- Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 4725 - 4728
(2010/07/04)
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- A bio-inspired copper catalyst system for practical catalytic cyanation of aryl bromides
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A general and environmentally improved protocol for the cyanation of aryl halides with the nontoxic cyanide source potassium hexacyanoferrate(II) {K 4[Fe(CN)6]} using copper catalysis and a ligand system based on 1-alkyl-1H-imidazoles is presented. The advantages of this system are a wide substrate range, high selectivity, easy handling, and inexpensive reagents.
- Schareina, Thomas,Zapf, Alexander,Cotte, Alain,Mueller, Nikolaus,Beller, Matthias
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experimental part
p. 3351 - 3355
(2009/06/06)
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- A state-of-the-art cyanation of aryl bromides: A novel and versatile copper catalyst system inspired by nature
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A general protocol for the cyanation of aryl halides with the nontoxic cyanide source K4[Fe(CN)6] using copper catalysis and a ligand system based on 1-alkylimidazoles is presented. The advantages of this system are the high selectivity, a unique substrate range, easy handling, and inexpensive reagents.
- Schareina, Thomas,Zapf, Alexander,Maegerlein, Wolfgang,Mueller, Nikolaus,Beller, Matthias
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p. 6249 - 6254
(2008/02/13)
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- An environmentally benign procedure for the Cu-catalyzed cyanation of aryl bromides
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The development of a general Cu-catalyzed synthesis of (hetero)aromatic nitriles from the corresponding aryl bromides and potassium hexacyanoferrate(II) is described. This novel protocol avoids the use of highly toxic alkali cyanides and precious palladium catalysts. Best results were achieved applying Cu(BF4)2?6H2O (0.1 equiv) and N,N′-dimethyl ethylenediamine (DMEDA; 1.0 equiv) in N,N-dimethyl acetamide (DMAc).
- Schareina, Thomas,Zapf, Alexander,Beller, Matthias
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p. 2585 - 2588
(2007/10/03)
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- Improving palladium-catalyzed cyanation of aryl halides: Development of a state-of-the-art methodology using potassium hexacyanoferrate(II) as cyanating agent
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Benzonitriles are easily accessible via palladium-catalyzed cyanation of aryl halides using potassium hexacyanoferrate(II) as cyanide source. This method is applicable on both activated and deactivated aryl and heteroaryl bromides and activated chlorides giving the corresponding benzonitriles in good to excellent yield. Advantageously, the used cyanating agent is non-toxic and cheap. The presented catalyst system is rather simple and it is not necessary to add expensive phosphines, making the novel method also attractive for industrial applications. Benzonitriles are easily accessible via palladium-catalyzed cyanation of aryl halides using potassium hexacyanoferrate(II) as cyanide source. This method is applicable on both activated and deactivated aryl and heteroaryl bromides and activated chlorides giving the corresponding benzonitriles in good to excellent yield. Advantageously, the used cyanating agent is non-toxic and cheap. The presented catalyst system is rather simple and it is not necessary to add expensive phosphines, making the novel method also attractive for industrial applications.
- Schareina, Thomas,Zapf, Alexander,Beller, Matthias
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p. 4576 - 4583
(2007/10/03)
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- Utilization of a peptide lead for the discovery of a novel PTP1B-binding motif
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Examination of the PTP1B inhibitory potency of an extensive series of phosphotyrosyl (pTyr) mimetics (Xxx) expressed in the EGFr-derived hexapeptide platform Ac-Asp-Ala-Asp-Xxx-Leu-amide previously led to the finding of high inhibitory potency when Xxx = 4-(phosphonodifluoromethyl)phenylalanyl (F2Pmp) (Ki = 0.2 μM) and when Xxx = 3-carboxy-4-carboxy-methyloxyphenylalanyl (Ki = 3.6 μM). In the first instance, further work led from the F2Pmp-containing peptide to monomeric inhibitor, 6-(phosphonodifluoromethyl)-2-naphthoic acid (Ki = 22 μM), and to the pseudo-dipeptide mimetic, N-[6-(phosphonodifluoromethyl)-2-naphthoyl]-glutamic acid (Ki = 12 μM). In the current study, a similar approach was applied to the 3-carboxy-4-carboxymethyloxyphenylalanyl-containing peptide, which led to the preparation of monomeric 5-carboxy-6-carboxymethyloxy-2-naphthoic acid (Ki = 900 μM). However, contrary to expectations based on the aforementioned F2Pmp work, incorporation of this putative pTyr mimetic into the pseudo-dipeptide, N-[5-carboxy-6-carboxymethyloxy-2-naphthoyl]-glutamic acid, resulted in a substantial loss of binding affinity. A reevaluation of binding orientation for 5-carboxy-6-carboxymethyloxy-2-naphthoic acid was therefore undertaken, which indicated a 180° reversal of the binding orientation within the PTP1B catalytic site. In the new orientation, the naphthyl 2-carboxyl group, and not the o-carboxy carboxymethyloxy groups, mimics a phosphoryl group. Indeed, when 5-carboxy-2-naphthoic acid itself was examined at neutral pH for inhibitory potency, it was found to have Ki = 31 ± 7 μM, which is lower than parent 5-carboxy-6-carboxymethyloxy-2-naphthoic acid. In this fashion, 5-carboxy-2-naphthoic acid (or more appropriately, 6-carboxy-1-naphthoic acid) has been identified as a novel PTP1B binding motif.
- Gao,Voigt,Zhao,Pais,Zhang,Wu,Zhang,Burke Jr.
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p. 2869 - 2878
(2007/10/03)
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- Synthesis, transition temperatures, and optical properties of various 2,6-disubstituted naphthalenes and related 1-benzothiophenes with butylsulfanyl and cyano or isothiocyanato terminal groups
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Fourteen compounds based on 2,6-disubstituted naphthalenes or related 1-benzothiophene moieties with butylsulfanyl and cyano or isothiocyanato terminal groups have been synthesised. The transition temperatures of the compounds and their refractive indices have been determined and the derived values for the optical anisotropies, polarisabilities and order parameters have been calculated. With one exception (which also shows a smectic A phase), all the compounds with naphthyl and phenyl groups are solely nematogenic; for these compounds the naphthyl unit gives an average increase in T(N-I) value and melting point of 72 and 20°C respectively compared to the values for the compounds with a phenyl in place of the naphthyl unit. The incorporation of a 2,5-thiophene unit in place of phenyl lowers T(N-I) and when it is part of a 1-benzothiophene unit the depression is even greater. The naphthalene compounds increase the values of optical anisotropy by approximately 0.04, compared to the phenyl systems, mainly because they increase the refractive index of the e-ray (n values); compound 12 has an exceptionally high optical anisotropy (Δn value) of 0.54.
- Seed,Toyne,Goodby,Hird
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p. 2069 - 2080
(2007/10/03)
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