- Photocycloaddition of Cyanonaphthalenes to 1,3-Cyclohexadiene
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To prevent secondary processes due to facile thermal reaction, low-temperature irradiations of cyanonaphthalenes and 1,3-cyclohexadiene through a Pyrex filter were conducted. Along with the identification of the products, the results of the triplet-sensitized photoreaction of the irradiated mixture, low-temperature 1H NMR study of the irradiated mixture, and the Cope rearrangement reaction of some products suggested that the primary major products are the corresponding exo-[4 + 4] adducts fused at 1,4 position of the naphthalene skeleton and the syn-[2 + 2] adducts fused at 1,2 position. The formations of the primary products in these singlet-state photocycloaddition reactions were interpreted by primary and secondary orbital interactions. A rationalization for the previous results on the photoreactions at room temperature was also provided.
- Noh, Taehee,Kim, Daekyun,Kim, Yong-Jae
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- β-naphthalene incorporated thiazole-5-carboxamides/thiazole -5- ketones: Design, synthesis and anticonvulsant screening against two seizure models
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A bunch of β-naphthalene incorporated thiazole-5-carboxamides/thiazole -5- ketones (7a-7o& 8a-8e) were prepared by reacting 4-methyl-2-(naphthalen-2-yl)thiazole-5-carbonyl chloride with appropriate amines. Structures of all the compounds were explained by elemental analysis, FT-IR, 1H NMR and mass spectral data. The compounds were evaluated for their anticonvulsant activity employing MES and chemoshock (scPTZ) seizure tests. Neurotoxicity was also assessed. Majority of these compounds exhibited significant activity against both animal models; however, compounds 7e, 7j, 7n and 8c displayed promising activity and could be considered as leads for further investigations.
- Arshad, Mohammed Faiz,Al-Otaibi, Faisal,Mustafa, Gulam,Shousha, Saad,Alshahrani, Abdulrahman
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- Photoinduced Electron Transfer Reaction of Mono- and Dicyanonaphthalenes with Allyltrimethylsilane: Synthesis of Benzotricyclo3,8>nonenes by Reductive Photoallylation and Intramolecular (2? + 2?) Photocycloaddition
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Irradiation of an acetonitrile-methanol (4:1) solution containing 1-cyanonaphthalene and allyltrimethylsilane (1) through Pyrex filter (>280 nm) regioselectively gave 3-cyano-4,5-benzotricyclo3,8>-4-nonene.The photoreaction of 2-cyanonaphthalene, 1-cyano-2-methylnaphthalene, 1-cyano-4-methylnaphthalene, 1,5- and 2,3-dicyanonaphthalenes with 1 gave the corresponding benzotricyclic compounds also in a regioselective manner.However, the photorection of 2,3-disubstituted 1,4-dicyanonaphthalenes with 1 gave no benzotricyclic compounds, but only the allyl substitution and reductive allylation products.These photoreactions were initiated by photoinduced electron transfer from 1 to the excited singlet states of mono- and dicyanonaphthalenes.The reductive allylation products from the former cyanonaphthalenes afforded the benzotricyclic compounds by an intramolecular (2? + 2?) photocycloaddition in good yields.The regioselectivity in the allylation reaction is discussed on the basis of the results of MO calculations of the radical anions of mono- and dicyanonaphthalenes.
- Nishiyama, Toshinori,Mizuno, Kazuhiko,Otsuji, Yoshio,Inoue, Hiroo
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- Concentration-dependent isotope effects. The photocyanation of naphthalene
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Concentration-dependent isotope effects (IEs) were measured in the competitive photocyanation of naphthalene and perdeuterionaphthalene in acetonitrile in the presence of electron acceptors. The concentration of the reagents naphthalene, cyanide, and oxygen influences the magnitude of the IE. Experiments in which the photocyanation is brought about via selective excitation of an electron acceptor show that the naphthalene-concentration dependence of the IEs is not caused by the naphthalene radical cations, which are intermediates in the photoreaction. This is corroborated by an electrochemical study of (the reactivity of) these radical cations. From these observations and complementary semiempirical PM3 calculations it is concluded that the variation of the IE with naphthalene concentration is due to an excited-state equilibration. A detailed reaction mechanism is proposed to account for the observed IEs.
- Zuilhof, Han,Van Gelderen, Frans A.,Cornelisse, Jan,Lodder, Gerrit
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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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- Cyanide-Free Cyanation of Aryl Iodides with Nitromethane by Using an Amphiphilic Polymer-Supported Palladium Catalyst
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A cyanide-free aromatic cyanation was developed that uses nitromethane as a cyanide source in water with an amphiphilic polystyrene poly(ethylene glycol) resin-supported palladium catalyst and an alkyl halide (1-iodobutane). The cyanation proceeds through the palladium-catalyzed cross-coupling of an aryl halide with nitromethane, followed by transformation of the resultant (nitromethyl)arene intermediate into a nitrile by 1-iodobutane.
- Niimi, Ryoko,Suzuka, Toshimasa,Uozumi, Yasuhiro
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supporting information
p. 40 - 44
(2021/11/30)
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- 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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- Development of Potent 3-Br-isoxazoline-Based Antimalarial and Antileishmanial Compounds
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Starting from the structure of previously reported 3-Br-isoxazoline-based covalent inhibitors of P. falciparum glyceraldehyde 3-phosphate dehydrogenase, and with the intent to improve their metabolic stability and antimalarial activity, we designed and synthesized a series of simplified analogues that are characterized by the insertion of the oxadiazole ring as a bioisosteric replacement for the metabolically labile ester/amide function. We then further replaced the oxadiazole ring with a series of five-membered heterocycles and finally combined the most promising structural features. All the new derivatives were tested in vitro for antimalarial as well as antileishmanial activity. We identified two very promising new lead compounds, endowed with submicromolar antileishmanial activity and nanomolar antiplasmodial activity, respectively, and a very high selectivity index with respect to mammalian cells.
- Galbiati, Andrea,Zana, Aureliano,Coser, Consuelo,Tamborini, Lucia,Basilico, Nicoletta,Parapini, Silvia,Taramelli, Donatella,Conti, Paola
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supporting information
p. 1726 - 1732
(2021/11/01)
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- Efficient nitriding reagent and application thereof
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The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
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Paragraph 0239-0241
(2021/03/31)
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- Novel chalcone/aryl carboximidamide hybrids as potent anti-inflammatory via inhibition of prostaglandin E2 and inducible NO synthase activities: design, synthesis, molecular docking studies and ADMET prediction
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Two series of chalcone/aryl carboximidamide hybrids 4a–f and 6a–f were synthesised and evaluated for their inhibitory activity against iNOS and PGE2. The most potent derivatives were further checked for their in?vivo anti-inflammatory activity utilising carrageenan-induced rat paw oedema model. Compounds 4c, 4d, 6c and 6d were proved to be the most effective inhibitors of PGE2, LPS-induced NO production, iNOS activity. Moreover, 4c, 4d, 6c and 6d showed significant oedema inhibition ranging from 62.21% to 78.51%, compared to indomethacin (56.27 ± 2.14%) and celecoxib (12.32%). Additionally, 4c, 6a and 6e displayed good COX2 inhibitory activity while 4c, 6a and 6c exhibited the highest 5LOX inhibitory activity. Compounds 4c, 4d, 6c and 6d fit nicely into the pocket of iNOS protein (PDB ID: 1r35) via the important amino acid residues. Prediction of physicochemical parameters exhibited that 4c, 4d, 6c and 6d had acceptable physicochemical parameters and drug-likeness. The results indicated that chalcone/aryl carboximidamides 4c, 4d, 6c and 6d, in particular 4d and 6d, could be used as promising lead candidates as potent anti-inflammatory agents.
- Ibrahim, Tarek S.,Moustafa, Amr H.,Almalki, Ahmad J.,Allam, Rasha M.,Althagafi, Abdulhamid,Md, Shadab,Mohamed, Mamdouh F. A.
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p. 1067 - 1078
(2021/05/28)
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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 0093-0095
(2021/06/21)
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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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- Development and Molecular Understanding of a Pd-Catalyzed Cyanation of Aryl Boronic Acids Enabled by High-Throughput Experimentation and Data Analysis
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A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.
- De Jesus Silva, Jordan,Bartalucci, Niccolò,Jelier, Benson,Grosslight, Samantha,Gensch, Tobias,Schünemann, Claas,Müller, Bernd,Kamer, Paul C. J.,Copéret, Christophe,Sigman, Matthew S.,Togni, Antonio
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- Imidazole hydrochloride promoted synthesis of 3,5-disubstituted-1,2,4-oxadiazoles
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Imidazole hydrochloride as an additive promotes the reaction of amidoximes and DMA derivatives to generated 3,5-disubstituted-1,2,4-oxadiazoles in low to excellent yields without the use of coupling reagents, oxidants, strong acids or bases and other additives.
- Wang, Xuetong,Wang, Yin,Liu, Xiaoling,He, Tingshu,Li, Lingli,Wu, Huili,Zhou, Shangjun,Li, Dan,Liao, Siwei,Xu, Ping,Huang, Xing,Yuan, Jianyong
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- Nickel-Catalyzed Cyanation of Aryl Thioethers
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A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.
- Delcaillau, Tristan,Woenckhaus-Alvarez, Adrian,Morandi, Bill
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supporting information
p. 7018 - 7022
(2021/09/13)
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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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- Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
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A copper-promoted cyanation of aryl iodides has been successfully developed by using N,N-dimethyl aminomalononitrile as the cyanide source with moderate toxicity and better stability. This reaction features broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.
- Liu, Si-Zhan,Li, Jing,Xue, Cao-Gen,Xu, Xue-Tao,Lei, Lin-Sheng,Huo, Chen-Yu,Wang, Zhen,Wang, Shao-Hua
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supporting information
(2021/02/01)
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- Iodine Promoted Conversion of Esters to Nitriles and Ketones under Metal-Free Conditions
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We report a novel strategy to prepare valuable nitriles and ketones through the conversion of esters under metal-free conditions. By using the I2/PCl3 system, various substrates including aliphatic and aromatic esters could react with acetonitrile and arenes to afford the desired products in good to excellent yields. This method is compatible with a number of functional groups and provides a simple and practical approach for the synthesis of nitrile compounds and aryl ketones.
- Xiao, Jing,Guo, Fengzhe,Li, Yinfeng,Li, Fangshao,Li, Qiang,Tang, Zi-Long
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p. 2028 - 2035
(2021/02/03)
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- CuO-catalyzed conversion of arylacetic acids into aromatic nitriles with K4Fe(CN)6 as the nitrogen source
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Readily available CuO was demonstrated to be effective as the catalyst for the conversion of arylacetic acids to aromatic nitriles with non-toxic and inexpensive K4Fe(CN)6 as the nitrogen source via the complete cleavage of the C[tbnd]N triple bond. The present method allowed a series of arylacetic acids including phenylacetic acids, naphthaleneacetic acids, 2-thiopheneacetic acid and 2-furanacetic acid to be converted into the targeted products in low to high yields.
- Ren, Yun-Lai,Shen, Zhenpeng,Tian, Xinzhe,Xing, Ai-Ping,Zhao, Zhe
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- Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
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There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
- Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
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p. 6299 - 6308
(2020/07/21)
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- Earth-Abundant Bimetallic Nanoparticle Catalysts for Aerobic Ammoxidation of Alcohols to Nitriles
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Heterogeneous nitrogen-doped carbon-incarcerated iron/copper bimetallic nanoparticle (NP) catalysts prepared from nitrogen-containing polymers were developed. These catalysts showed activity higher than that of the corresponding monometallic NPs for aerobic ammoxidation of alcohols to nitriles. The important procedure for high activity in the catalyst preparation was found to be a simultaneous reduction of two metal salts.
- Kobayashi, Shu,Yang, Xi,Yasukawa, Tomohiro
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p. 7543 - 7548
(2020/06/27)
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- On-Demand Generation and Use in Continuous Synthesis of the Ambiphilic Nitrogen Source Chloramine
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Herein, we demonstrate the on-demand synthesis of chloramine from aqueous ammonia and sodium hypochlorite solutions, and its subsequent utilization as an ambiphilic nitrogen source in continuous-flow synthesis. Despite its advantages in cost and atom economy, chloramine has not seen widespread use in batch synthesis due to its unstable and hazardous nature. Continuous-flow chemistry, however, provides an excellent platform for generating and handling chloramine in a safe, reliable, and inexpensive manner. Unsaturated aldehydes are converted to valuable aziridines and nitriles, and thioethers are converted to sulfoxides, in moderate to good yields and exceedingly short reaction times. In this telescoped process, chloramine is generated in situ and immediately used, providing safe and efficient conditions for reaction scale-up while mitigating the issue of its decomposition over time.
- Danahy, Kelley E.,Styduhar, Evan D.,Fodness, Aria M.,Heckman, Laurel M.,Jamison, Timothy F.
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supporting information
p. 8392 - 8395
(2020/11/18)
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- HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
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We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
- Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
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supporting information
p. 4161 - 4164
(2020/07/14)
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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 0070; 0071
(2020/09/12)
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
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supporting information
p. 281 - 285
(2020/01/28)
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- Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles
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Chlorotropylium chloride as a catalyst for the transformations of oximes, ketones, and aldehydes to their corresponding amides and nitriles in excellent yields (up to 99 %) and in short reaction times (mostly 10–15 min). Oximes were electrophilically attacked on the hydroxyl oxygen by chlorotropylium. The produced tropylium oxime ethers were the key intermediates, of which the ketoxime ether led to amide through Beckmann rearrangement, and the aldoxime ether led to nitrile by nitrogen base DBU assisted formal dehydration. This chlorotropylium activation protocol offered general, mild, and efficient avenues bifurcately from oximes to both amides and nitriles by one organocatalyst.
- Xu, Jiaxi,Gao, Yu,Li, Zhenjiang,Liu, Jingjing,Guo, Tianfo,Zhang, Lei,Wang, Haixin,Zhang, Zhihao,Guo, Kai
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p. 311 - 315
(2020/01/25)
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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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- 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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- An Efficient Synthesis of Nitriles from Aldoximes in the Presence of Trifluoromethanesulfonic Anhydride in Mild Conditions
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Abstract: A new and convenient protocol has been proposed for the transformation of aldoximes to nitriles using trifluoromethanesulfonic anhydride and triethylamine. The proposed method allows a range of aldoximes, including aromatic, heterocyclic, aliphatic, and cycloaliphatic aldoximes, to be converted to the corresponding nitriles in good to excellent yields.
- Uludag, N.
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p. 1640 - 1645
(2020/10/22)
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- Nickel-catalyzed aminocarbonylation of Aryl/Alkenyl/Allyl (pseudo)halides with isocyanides and H2O
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Herein described is a nickel-catalyzed aminocarbonylation of aryl/alkenyl/allyl (pseudo)halides with isocyanides, providing aryl/alkenyl/allyl amides in 41% to 92% yields. Functional groups such as F, Cl, OMe, and heteroaromatic rings are compatible in the reaction. A Ni(0)/Ni(II) catalytic cycle is proposed based on preliminary experiments and previous literature. The reaction features readily available nickel salt, broad functional group tolerance, and simple reaction conditions.
- Li, Qiao,Cai, Yun,Jin, Hongwei,Liu, Yunkui,Zhou, Bingwei
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supporting information
(2020/11/27)
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- Synthesis of nitriles via the iodine-mediated dehydrosulfurization of thioamides
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A simple general method for the synthesis of nitriles using the inexpensive and easy to handle iodine (I2) is described herein. The reaction of thioamides with I2 in the presence of triethylamine at room temperature under aerobic conditions afforded various nitriles bearing aryl, vinyl, and alkyl groups in good-to-excellent yields. This method was also effective for conversion from thioureas to cyanamides.
- Murata, Yuki,Iwasa, Hitomi,Matsumura, Mio,Yasuike, Shuji
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p. 679 - 681
(2020/07/30)
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- Difluorocarbene-Based Cyanation of Aryl Iodides
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A large number of efficient cyanation methods have been developed because of the wide range of applications of nitriles, but conventional methods usually suffer from the need for a toxic cyanation reagent. Although difluorocarbene chemistry has received increasing attention, the use of difluorocarbene as a sources of the nitrile carbon for nitrile groups remains largely unexplored. We describe a difluorocarbene-based cyanation of aryl iodides promoted by a cheap copper source, Cu(NO 3) 2 ·2.5H 2 O, under an air atmosphere. Ph 3 P + CF 2 CO 2-, an easily available and shelf-stable difluorocarbene reagent, and NaNH 2 are used as the carbon source and the nitrogen source for the nitrile group, respectively. The cyanation protocol is attractive because no toxic reagent is used and performing the reactions under an air atmosphere is operationally convenient.
- Cao, Yu-Cai,Du, Ruo-Bing,Fu, Zhi-Hong,Guo, Yu,Lin, Jin-Hong,Xiao, Ji-Chang,Xiao, Xuan,Yao, Xu,Zhang, Yin-Xiang,Zheng, Xing
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supporting information
p. 713 - 717
(2020/04/08)
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- Organophotoredox assisted cyanation of bromoarenes: via silyl-radical-mediated bromine abstraction
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The insertion of a nitrile (-CN) group into arenes through the direct functionalization of the C(sp2)-Br bond is a challenging reaction. Herein, we report an organophotoredox method for the cyanation of aryl bromides using the organic photoredox catalyst 4CzIPN and tosyl cyanide (TsCN) as the nitrile source. A photogenerated silyl radical, via a single electron transfer (SET) mechanism, was employed to abstract bromine from aryl bromide to provide an aryl radical, which was concomitantly intercepted by TsCN to afford the aromatic nitrile. A range of substrates containing electron-donating and -withdrawing groups was demonstrated to undergo cyanation at room temperature in good yields.
- Shah, Sk. Sheriff,Shee, Maniklal,Singh, N. D. Pradeep
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supporting information
p. 4240 - 4243
(2020/04/22)
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- Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
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We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
- Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
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p. 1397 - 1405
(2020/02/04)
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- Ionic-Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles
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Unprecedented in literature, the conversion of aryl alkenes into β-nitrostyrenes (2) or benzonitriles (3) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium-based ILs, such as [Bmim]Cl, that favor the C–H nitration leading to β-nitrostyrenes, while tetraalkylammonium-based ILs, such as TBAA, privilege the C=C bond cleavage affording benzonitriles. Besides a substrate scope, mechanistic hypotheses were provided on the origin of the different selectivity in the two kinds of ILs, based on their own tunable properties such as polarity, viscosity, and solvent cage effects.
- Casiello, Michele,Caputo, Daniela,Fusco, Caterina,Cotugno, Pietro,Rizzi, Vito,Dell'Anna, Maria Michela,D'Accolti, Lucia,Nacci, Angelo
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supporting information
p. 6012 - 6018
(2020/08/24)
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- Visible-light-mediated borylation of aryl and alkyl halides with a palladium complex
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Palladium catalyzed visible-light-mediated borylation of inactivated aryl and alkyl halides is reported; the method provided high yields and excellent functional group compatibility. Furthermore, arylsilicates were synthesized selectively using dimethylphenylsilyl boronic ester via changing the reaction conditions. Finally, the possible reaction mechanism is determined through fluorescence quenching and turn on/off experiments.
- Zhao, Jia-Hui,Zhou, Zhao-Zhao,Zhang, Yue,Su, Xuan,Chen, Xi-Meng,Liang, Yong-Min
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supporting information
p. 4390 - 4394
(2020/10/20)
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- Dehydrogenation of Primary Alkyl Azides to Nitriles Catalyzed by Pincer Iridium/Ruthenium Complexes
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Pincer metal complexes exhibit superior catalytic activity in the dehydrogenation of plain alkanes, but find limited application in the dehydrogenation of functionalized organic molecules. Starting from easily accessible primary alkyl azides, here we report an efficient dehydrogenation of azides to nitriles using pincer iridium or ruthenium complexes as the catalysts. This method offers a route to cyanide-free preparation of nitriles without carbon chain elongation and without the use of strong oxidants. Both benzyl and linear aliphatic azides can be dehydrogenated with tert-butylethylene as the hydrogen acceptor to afford nitriles in moderate to high yields. Various functional groups can be tolerated, and the H?C?C?H bond dehydrogenation does not occur for linear alkyl azide substrates. Furthermore, the pincer Ir catalytic system was found to catalyze the direct azide dehydrogenation without the use of a sacrificial hydrogen acceptor.
- Gan, Lan,Jia, Xiangqing,Fang, Huaquan,Liu, Guixia,Huang, Zheng
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p. 3661 - 3665
(2020/06/02)
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- Iron-Promoted Decarboxylation of Arylacetic Acids for the Synthesis of Aromatic Nitriles with Sodium Nitrite as the Nitrogen Source
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A new and effective method was developed for the synthesis of aromatic nitriles from arylacetic acids by using NaNO 2as the nitrogen source and Fe(OTf) 3as the promoter at 50 °C. A series of arylacetic acids underwent this transformation to give the targeted products in yields of 51-90%. Because of the mild conditions, the reaction is compatible with a broad range of functional groups, including ester, carboxy, hydroxy, acetamido, halo, nitro, cyano, methoxy, and even highly reactive formyl groups.
- Shen, Zhenpeng,Liu, Wenbo,Tian, Xinzhe,Zhao, Zhe,Ren, Yun-Lai
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supporting information
p. 1805 - 1808
(2020/11/02)
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- Ligand-Promoted Non-Directed C?H Cyanation of Arenes
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This article reports the first example of a 2-pyridone accelerated non-directed C?H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (kH/kD=4.40) indicates that the C?H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.
- Liu, Luo-Yan,Yeung, Kap-Sun,Yu, Jin-Quan
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supporting information
p. 2199 - 2202
(2019/01/24)
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- Visible-light-driven catalytic oxidation of aldehydes and alcohols to nitriles by 4-acetamido-tempo using ammonium carbamate as a nitrogen source
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A mild and efficient route to prepare nitriles from aldehydes by combining photoredox catalysis with oxoammonium cations is reported. The reaction is performed using ammonium carbamate as the nitrogen source. The practicality of the method is increased by the extension of the dual catalytic system to one-pot two-step conversion of alcohols to nitriles.
- Nandi, Jyoti,Leadbeater, Nicholas E.
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supporting information
p. 9182 - 9186
(2019/11/05)
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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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p. 3190 - 3194
(2019/05/21)
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- Visible light-induced direct conversion of aldehydes into nitriles in aqueous medium using Co@g-C3N4 as photocatalyst
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Unprecedented Co@g-C3N4 catalyzed visible light driven efficient conversion of a variety of aldehydes into corresponding nitriles is reported. Operational simplicity, excellent yield of pure products (87–94%), ambient reaction condition, using aqueous methanol as solvent, visible-light photocatalysis are the salient features of envisaged methodology for direct conversion of aldehydes into nitriles. Furthermore, reusability of Co@g-C3N4 was checked up to five runs and it was noticed that there was no substantial change in morphology as well as the catalytic efficiency of catalyst.
- Verma, Fooleswar,Shukla, Prashant,Bhardiya, Smita R.,Singh, Manorama,Rai, Ankita,Rai, Vijai K.
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- Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
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A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
- Fang, Wan-Yin,Qin, Hua-Li
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p. 5803 - 5812
(2019/05/14)
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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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- Method for preparing nitrile from primary amide
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The invention relates to a method for preparing nitrile from primary amide, which has a structural formula as shown in the specification. The method comprises the following steps: sequentially addingdimethyl sulfoxide (0.01 equiv), primary amide (1.0 equiv) and triethylamine (2.5 equiv) into acetonitrile at room temperature; dropwise adding oxalyl chloride (1.2 equiv) into the acetonitrile solution, and reacting for 40-60 minutes to obtain a corresponding nitrile compound having the yield of 80-96 percent.
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-
Paragraph 0012; 0013
(2019/01/21)
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- Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
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Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
- Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
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supporting information
p. 19257 - 19262
(2019/12/02)
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- Transformation of aromatic bromides into aromatic nitriles with n-BuLi, pivalonitrile, and iodine under metal cyanide-free conditions
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Various aromatic nitriles could be obtained in good yields by the treatment of aryl bromides with n-butyllithium and then pivalonitrile, followed by the treatment with molecular iodine at 70 °C, without metal cyanides under transition-metal-free conditions. The present reaction proceeds through the radical β-elimination of imino-nitrogen-centered radicals formed from the reactions of imines and N-iodoimines under warming conditions.
- Uchida, Ko,Togo, Hideo
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- Nickel-Catalyzed Decarbonylative Cyanation of Acyl Chlorides
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Ni-catalyzed decarbonylative cyanation of acyl chlorides with trimethylsilyl cyanide has been achieved. This transformation is applicable to the synthesis of an array of nitrile compounds bearing a wide range of functional groups under neutral conditions. The step-by-step experimental studies revealed that the reaction sequences of the present catalytic reaction are oxidative addition, transmetalation, decarbonylation, and reductive elimination.
- Wang, Zhenhua,Wang, Xiu,Ura, Yasuyuki,Nishihara, Yasushi
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supporting information
p. 6779 - 6784
(2019/08/26)
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- Direct c-h/c-h cross-coupling of benzimidates with heteroarenes to access biheteroaryl-2-carbonitriles
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A Rh-catalyzed C-H/C-H oxidative cross-coupling reaction of benzimidates with heteroarenes is developed, yielding biheteroaryl-2-carbonitriles directly after in situ dealcoholization. This protocol features high atom- and step-economy, and a broad substrate scope with good functional group tolerance.
- Wang, Zhigang,Wang, Fei,Liu, Zheng,He, Shuang,Pu, Xingwen,Yang, Yudong,Gao, Ge
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supporting information
p. 10599 - 10602
(2019/09/06)
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- Iron and Phenol Co-Catalysis for Rapid Synthesis of Nitriles under Mild Conditions
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A mild, scalable, high yielding, and rapid route to access diverse nitriles from aldehyde oxime esters enabled by iron(III) and phenol co-catalysis has been developed. The reaction was performed at room temperature to give nitriles in excellent yield within minutes. Mechanistic studies show that the reaction may proceed through a radical process in which benzoyl aldehyde oxime is not only a substrate, but also an ancillary ligand to support iron salt in the promotion of the transformation.
- Meng, Hong,Gao, Sen,Luo, Meiming,Zeng, Xiaoming
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p. 4617 - 4623
(2019/07/15)
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- Pd(II)-immobilized on a nanoporous triazine-based covalent imine framework for facile cyanation of haloarenes with K4Fe(CN)6
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A porous covalent organic framework incorporated with both imine and triazine functionalities (TPA-TCIF) was synthesized by Schiff-base condensation of 2,4,6-tris(4-aminophenyl)triazine and tris(4-formylphenyl)amine under the solvothermal condition of a 1-butanol:1,2-dichlorobenzene mixture. The resulting TPA-TCIF was a highly ordered crystalline network with surface area of 2938 m2 g?1, which was among the highest reported imine-based porous covalent organic frameworks. TPA-TCIF was also stable in water and other organic solvents. Pd(II) was immobilized into TPA-TCIF network and the resultant Pd/TPA-TCIF was tested as a catalyst for the additive-free cyanation of haloarenes with non-toxic K4[Fe(CN)6]. The catalyst showed excellent catalytic activity, and both electron-donating / -withdrawing groups attached to the para- and meta-positions of bromoarenes produced the respective nitriles with good to excellent yields. The catalyst could be reused up to five times without noticeable loss of activity or catalyst poisoning by cyanide ions during the reaction.
- Puthiaraj, Pillaiyar,Yu, Kwangsun,Shim, Sang Eun,Ahn, Wha-Seung
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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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