- Antimicrobial volatile glucosinolate autolysis products from Hornungia petraea (L.) Rchb. (Brassicaceae)
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Plant samples of Hornungia petraea were analyzed for glucosinolate (GLS) autolysis metabolites for the first time. GC-MS analysis of the autolysate and the synthesis of a series (12 compounds) of possible glucosinolate breakdown products revealed/corroborated the presence of glucoaubrietin, glucolimnanthin, glucolepigramin and glucotropaeolin in this species as the most likely "mustard oil" precursors. GLS degradation products identified in the autolysate of H. petraea, benzyl isothiocyanate, 3- and 4-methoxybenzyl isothiocyanate, along with several other structurally related compounds were evaluated for antimicrobial activity in order to possibly pinpoint the role of the latter secondary metabolites in the plant tissues. The assays showed a very high antibacterial activity of the tested isothiocyanates against Sarcina lutea and an antifungal effect against Aspergillus fumigatus and Candida albicans with MIC values in the order of 1 μg/ml value.
- Radulovi?, Niko S.,Deki?, Milan S.,Stojanovi?-Radi?, Zorica Z.
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- PALLADIUM CATALYZED REACTION OF ARYL BROMIDES WITH CYANOMETHYLTRIBUTYLTIN. AROMATIC CYANOMETHYLATION
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Palladium catalyzed reaction of aryl bromides with cyanomethyltributyltin gave arylacetonitriles in moderate yields.Aryl bromides having strong electron-withdrawing groups (such as acyl, cyano, nitro, etc.) cannot be applied to the reaction.
- Kosugi, Masanori,Ishiguro, Masahiro,Negishi, Yoshikazu,Sano, Hiroshi,Migita, Toshihiko
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- Conversion of Alcohols, Thiols, and Trimethysilyl Ethers to Alkyl Cyanides Using Triphenylphosphine/2,3-Dichlorol-5,6-dicyanobenzoquinone/n-Bu 4NCN
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Triphenylphosphine and 2,3-dichloro-5,6-dicyanobenzoquinone afford an adduct, which in the presence of n-Bu4NCN converts alcohols, thiols, and trimethylsilyl ethers into their corresponding alkyl cyanides in good to excellent yields at room tem
- Iranpoor, Nasser,Firouzabadi, Habib,Akhlaghinia, Batool,Nowrouzi, Najmeh
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- Synthesis of alkyl iodides/nitriles from carbonyl compounds using novel ruthenium tris(2,2,6,6-tetramethyl-3,5-heptanedionate) as catalyst
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Aldehydes and ketones were hydrogenated to the corresponding alcohols, which were then transformed in situ into their respective iodides and nitriles in good yields. A structurally well-defined O-containing transition metal complex, Ru (TMHD)3, was found to be the active catalyst for hydrogenation, iodination and cyanation reactions. It has high affinity for the transformation of benzylic alcohols to iodides and nitriles.
- Bhor, Malhari D.,Panda, Anil G.,Nandurkar, Nitin S.,Bhanage, Bhalchandra M.
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- Preparation of novel magnetic dicationic ionic liquid polymeric phase transfer catalyst and their application in nucleophilic substitution reactions of benzyl halides in water
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PEG-based magnetic dicationic ionic liquid was successfully prepared and evaluated as phase-transfer catalyst for nucleophilic substitution reactions of benzyl halides for the synthesis of benzyl azides and cyanides from good to excellent yields at 90 °C in water. The reactions occur in water and furnish the corresponding benzyl derivatives in high yields. No evidence for the formation of by-product for example benzyl alcohol of the reaction was observed and the products were obtained in pure form without further purification.
- Godajdar, Bijan Mombani,Ansari, Bita
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- A Facile Synthesis of Nitriles from 1-Nitro-1-alkenes by Electroreduction
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Electroreduction of 1-nitro-1-alkenes in the presence of titanium(IV) chloride affords nitriles in good yields.This procedure provides a facile transformation of aldehydes to one-carbon elongated nitriles since the 1-nitro-1-alkenes are best prepared from aldehydes and nitromethane.
- Sera, Akira,Tani, Hiroyuki,Nishiguchi, Ikuzo,Hirashima, Tsuneaki
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- Efficient conversion of tetrahydropyranyl (THP) ethers to their corresponding cyanides with triphenylphosphine/2,3-dichloro-5,6- dicyanobenzoquinone/n-Bu4 NCN
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Tetrahydropyranyl ethers were converted to their corresponding alkyl cyanides efficiently by using the triphenylphosphine/ 2,3-dichloro-5,6- dicyanobenoquinone / n-Bu4 NCN system in refluxing acetonitrile with good-to-excellent yields.
- Akhlaghinia, Batool
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- A simple one-pot procedure for the direct conversion of alcohols into alkyl nitriles using TsIm
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A convenient and efficient one-pot preparation of nitriles from alcohols using N-(p-toluenesulfonyl)imidazole (TsIm) is described. In this method, treatment of alcohols with a mixture of NaCN, TsIm and triethylamine in the presence of catalytic amounts of tetra-n-butylammonium iodide (TBAI) in refluxing DMF furnishes the corresponding alkyl nitriles in good yields. This methodology is highly efficient for various structurally diverse alcohols with selectivity for ROH: 1° > 2° > 3°.
- Soltani Rad, Mohammad Navid,Khalafi-Nezhad, Ali,Behrouz, Somayeh,Faghihi, Mohammad Ali
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- Nickel-Catalyzed Synthesis of Arylacetonitriles from Arylzinc Chlorides and Bromoacetonitrile
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Arylacetonitriles are synthesised by coupling arylzinc chlorides with bromoacetonitrile using Ni(acac)2/P(c-C6H11)(C6H5)2 as catalyst.The arylacetonitriles are reduced in situ with LiAlH4/AlCl3 to give the corresponding 2-aryl-1-aminoethanes.
- Frejd, Torbjoern,Klingstedt, Tomas
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- A heterogeneous palladium catalyst hybridised with a titanium dioxide photocatalyst for direct C-C bond formation between an aromatic ring and acetonitrile
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A palladium catalyst hybridised with a titanium dioxide photocatalyst can promote cyanomethylation of an aromatic ring by using acetonitrile, where the photocatalyst activates acetonitrile to form a cyanomethyl radical before the C-C bond formation using the palladium catalyst.
- Yoshida, Hisao,Fujimura, Yuki,Yuzawa, Hayato,Kumagai, Jun,Yoshida, Tomoko
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- Synthesis of heterocyclic ketene N,O-acetals from 5(2H)-isoxazolones
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Starting from 4-aryl isoxazolin-5-ones 1, a new synthesis of heterocyclic ketene N,O-acetals is described.
- Beccalli, Egle M.,Marchesini, Alessandro,Pilati, Tullio
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- Thermal Isomerizations of Substituted Benzyl Isocyanides: Relative Rates Controlled Entirely by Differences in Entropies of Activation
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The absolute and relative rates of thermal rearrangments of substituted benzyl isocyanides were obtained at the temperatures between 170 and 230 °C. The relative rates are independent of temperature and exhibit excellent Hammett correlations (p+ = -0.24). The temperature studies yielded activation parameters (ΔHY? and ΔSY?) and their differential counterparts (ΔΔHY-H? and ΔΔSY-H?). The differential terms were plotted against σ+. The secondary α-deuterium kinetic isotope effects (kD/kH = 1.11) were measured at several temperatures. The rate data can be rationalized with the cyclic TS. The substituent effects on the rates are due to the entropic contributions.
- Kim, Sung Soo,Choi, Won Jung,Zhu, Yu,Kim, Jin Hyun
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- 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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- 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 0111-0113
(2021/06/21)
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- Metal-Free Deoxygenation of Chiral Nitroalkanes: An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles
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A metal-free, mild and chemodivergent transformation involving nitroalkanes has been developed. Under optimized reaction conditions, in the presence of trichlorosilane and a tertiary amine, aliphatic nitroalkanes were selectively converted into amines or nitriles. Furthermore, when chiral β-substituted nitro compounds were reacted, the stereochemical integrity of the stereocenter was maintained and α-functionalized nitriles were obtained with no loss of enantiomeric excess. The methodology was successfully applied to the synthesis of chiral β-cyano esters, α-aryl alkylnitriles, and TBS-protected cyanohydrins, including direct precursors of four active pharmaceutical ingredients (ibuprofen, tembamide, aegeline and denopamine).
- Pirola, Margherita,Faverio, Chiara,Orlandi, Manuel,Benaglia, Maurizio
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supporting information
p. 10247 - 10250
(2021/06/18)
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- Assembly of α-(Hetero)aryl Nitriles via Copper-Catalyzed Coupling Reactions with (Hetero)aryl Chlorides and Bromides
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α-(Hetero)aryl nitriles are important structural motifs for pharmaceutical design. The known methods for direct synthesis of these compounds via coupling with (hetero)aryl halides suffer from narrow reaction scope. Herein, we report that the combination of copper salts and oxalic diamides enables the coupling of a variety of (hetero)aryl halides (Cl, Br) and ethyl cyanoacetate under mild conditions, affording α-(hetero)arylacetonitriles via one-pot decarboxylation. Additionally, the CuBr/oxalic diamide catalyzed coupling of (hetero)aryl bromides with α-alkyl-substituted ethyl cyanoacetates proceeds smoothly at 60 °C, leading to the formation of α-alkyl (hetero)arylacetonitriles after decarboxylation. The method features a general substrate scope and is compatible with various functionalities and heteroaryls.
- Chen, Ying,Xu, Lanting,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 7082 - 7086
(2021/02/26)
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- Direct C(sp3)-H Cyanation Enabled by a Highly Active Decatungstate Photocatalyst
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A highly efficient, direct C(sp3)-H cyanation was developed under mild photocatalytic conditions. The method enabled the direct cyanation of various C(sp3)-H substrates with excellent functional group tolerance. Notably, complex natural products and bioactive compounds were efficiently cyanated.
- Kim, Kunsoon,Lee, Seulchan,Hong, Soon Hyeok
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supporting information
p. 5501 - 5505
(2021/07/26)
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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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- Preparation method of alkyl nitrile compound
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The invention discloses a preparation method of an alkyl nitrile compound shown as formula I. The preparation method comprises the following step: in a solvent, in the presence of an additive, carrying out substitution reaction as shown in the specification on a cyanation reagent and an alkyl halide shown as formula II to obtain the alkyl nitrile compound shown as formula I, wherein the cyanationreagent is Zn (CN) 2 and/or Cu (CN) 2; the additive is one or more of an inorganic base, an organic base and a quaternary ammonium salt.
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Paragraph 0131-0133
(2020/05/14)
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- Lithiation Substitution of Unprotected Benzyltetrazoles
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1H-Tetrazoles occupy an important role in modern medicinal chemistry, but few methods for their modification exist. Many extant protocols require the use of a difficult to remove N-alkyl-protecting group, precluding the products from use as carboxylate bioisosteres, the major role of tetrazoles in pharmaceuticals. We herein report a convenient, protecting-group-free lithiation-substitution protocol for benzylic tetrazoles. Metalation with n-BuLi at 0 °C followed by electrophilic trapping gave a range of α-functionalized benzyltetrazoles in up to 91% yield.
- Wong, Jeff Y. F.,Lewandowska, Agnieszka,Trowse, Benjamin R.,Barker, Graeme
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supporting information
p. 7069 - 7072
(2019/09/30)
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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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- Double Dehydrogenation of Primary Amines to Nitriles by a Ruthenium Complex Featuring Pyrazole Functionality
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A ruthenium(II) complex bearing a naphthyridine-functionalized pyrazole ligand catalyzes oxidant-free and acceptorless selective double dehydrogenation of primary amines to nitriles at moderate temperature. The role of the proton-responsive entity on the ligand scaffold is demonstrated by control experiments, including the use of a N-methylated pyrazole analogue. DFT calculations reveal intricate hydride and proton transfers to achieve the overall elimination of 2 equiv of H2.
- Dutta, Indranil,Yadav, Sudhir,Sarbajna, Abir,De, Subhabrata,H?lscher, Markus,Leitner, Walter,Bera, Jitendra K.
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supporting information
p. 8662 - 8666
(2018/07/09)
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- Copper-Catalyzed Cyanation of N-Tosylhydrazones with Thiocyanate Salt as the "cN" Source
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A novel protocol for the synthesis of α-aryl nitriles has been successfully achieved via a copper-catalyzed cyanation of N-tosylhydrazones employing thiocyanate as the source of cyanide. The features of this method include a convenient operation, readily available substrates, low-toxicity thiocyanate salts, and a broad substrate scope.
- Huang, Yubing,Yu, Yue,Zhu, Zhongzhi,Zhu, Chuanle,Cen, Jinghe,Li, Xianwei,Wu, Wanqing,Jiang, Huanfeng
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p. 7621 - 7627
(2017/07/26)
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- One-Pot Preparation of C1-Homologated Aliphatic Nitriles from Aldehydes through a Wittig Reaction under Metal-Cyanide-Free Conditions
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A one-pot protocol to obtain C1-homologated aliphatic nitriles was achieved by treating aromatic and aliphatic aldehydes with the (methoxymethyl)triphenylphosphonium ylide followed by hydrolysis of the resulting methyl vinyl ethers with pTsOH (Ts = para-toluenesulfonyl) and treatment with molecular iodine and aqueous ammonia under metal cyanide free conditions. Neopentyl-type nitriles, which could not be obtained by conventional methods that involved conversion of the neopentyl alcohol into a tosylate and treatment with metal cyanide, were successfully obtained by using the present method.
- Ezawa, Masatoshi,Togo, Hideo
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p. 2379 - 2384
(2017/05/01)
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- Synthesis of Nitriles from Aldoximes and Primary Amides Using XtalFluor-E
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The dehydration reaction of aldoximes and amides for the synthesis of nitriles using [Et2NSF2]BF4 (XtalFluor-E) is described. Overall, the reaction proceeds rapidly (normally 1 h) at room temperature in an environmentally benign solvent (EtOAc) with only a slight excess of the dehydrating agent (1.1 equiv). A broad scope of nitriles can be prepared, including chiral nonracemic ones. In addition, in a number of cases, further purification of the nitrile after the workup was not required.
- Keita, Massaba,Vandamme, Mathilde,Paquin, Jean-Fran?ois
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p. 3758 - 3766
(2015/11/28)
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- The Concise Synthesis of Unsymmetric Triarylacetonitriles via Pd-Catalyzed Sequential Arylation: A New Synthetic Approach to Tri- and Tetraarylmethanes
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The selective synthesis of multiarylated acetonitriles via sequential palladium-catalyzed arylations of chloroacetonitrile is reported. The three aryl groups are installed via a Pd-catalyzed Suzuki-Miyaura cross coupling reaction followed by back-to-back C-H arylations to afford triarylacetonitriles in three steps with no over-arylation at any step. The triarylacetonitrile products can be converted into highly functionalized species including tetraarylmethanes. This new strategy provides rapid access to a variety of unsymmetrical tri- and tetraarylmethane derivatives from simple, readily available starting materials. (Chemical Presented)
- Nambo, Masakazu,Yar, Muhammad,Smith, Joel D.,Crudden, Cathleen M.
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supporting information
p. 50 - 53
(2015/07/28)
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- Two-step cyanomethylation protocol: Convenient access to functionalized aryl- and heteroarylacetonitriles
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A two-step protocol has been developed for the introduction of cyanomethylene groups to metalated aromatics through the intermediacy of substituted isoxazoles. A palladium-mediated cross-coupling reaction was used to introduce the isoxazole unit, followed by release of the cyanomethylene function under thermal or microwave-assisted conditions. The intermediate isoxazoles were shown to be amenable to further functionalization prior to deprotection of the sensitive cyanomethylene motif, allowing access to a wide range of aryl- and heteroaryl-substituted acetonitrile building blocks.
- Lindsay-Scott, Peter J.,Clarke, Aimee,Richardson, Jeffery
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supporting information
p. 476 - 479
(2015/03/05)
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- Synthesis of α-aryl esters and nitriles: Deaminative coupling of α-aminoesters and α-aminoacetonitriles with arylboronic acids
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Transition-metal-free synthesis of α-aryl esters and nitriles using arylboronic acids with α-aminoesters and α-aminoacetonitriles, respectively, as the starting materials has been developed. The reaction represents a rare case of converting C(sp3)-N bonds into C(sp3)-C(sp2) bonds. The reaction conditions are mild, demonstrate good functional-group tolerance, and can be scaled up. Touch base: A transition-metal-free protocol for the synthesis of α-aryl esters and nitriles by deaminative coupling is presented. Strong bases and transition-metal catalysts are not needed. The new synthetic method uses readily available starting materials and demonstrates wide substrate scope.
- Wu, Guojiao,Deng, Yifan,Wu, Chaoqiang,Zhang, Yan,Wang, Jianbo
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supporting information
p. 10510 - 10514
(2016/02/18)
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- Palladium-catalyzed methoxylation of aromatic chlorides with borate salts
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Herein we disclose a simple palladiumcatalyzed transformation for the methoxylation of aromatic chlorides with tetramethoxyborate salts. The procedure provides a new and efficient synthetic tool for the introduction of a methoxy group into aromatic systems. In addition, the reaction can be achieved using a wide range of aromatic and heteroaromatic chlorides, the cheapest class of halides.
- Tolnai, Gergely L.,Petho, Bálint,Králl, Péter,Nováka, Zoltán
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supporting information
p. 125 - 129
(2014/03/21)
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- Ionic liquid-induced conversion of methoxymethyl-protected alcohols into nitriles and iodides using [Hmim][NO3]
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This Letter reports a one-pot efficient conversion of methoxymethyl-ethers into their corresponding nitriles and iodides using the ionic liquid, 1-methyl-3H-imidazolium nitrate ([Hmim][NO3]) under microwave irradiation. A variety of products were prepared in high yields using this method.
- Noei, Jalil,Mirjafari, Arsalan
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supporting information
p. 4424 - 4426
(2014/08/05)
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- New approach to oximes through reduction of nitro compounds enabled by visible light photoredox catalysis
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A range of nitro compounds are smoothly reduced to their corresponding oximes under the synergistic effects of visible light irradiation, the Ru(bpy)3Cl2 photocatalyst, Hünig's base, Mg(ClO 4)2 activation, and MeCN solvent. This remarkably mild and environmentally benign protocol, when orchestrated with classical Beckmann rearrangement, enables such high-value industrial feedstock as caprolactam to be readily accessed from simple precursor nitrocyclohexane.
- Cai, Shunyou,Zhang, Shaolong,Zhao, Yaohong,Wang, David Zhigang
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p. 2660 - 2663
(2013/07/11)
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- Oxidant-free conversion of primary amines to nitriles
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An amide-derived NNN-Ru(II) hydride complex catalyzes oxidant-free, acceptorless, and chemoselective dehydrogenation of primary and secondary amines to the corresponding nitriles and imines with liberation of dihydrogen. The catalyst system tolerates oxidizable functionality and is selective for the dehydrogenation of primary amines (-CH2NH2) in the presence of amines without α-CH hydrogens.
- Tseng, Kuei-Nin T.,Rizzi, Andrew M.,Szymczak, Nathaniel K.
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supporting information
p. 16352 - 16355
(2013/12/04)
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- Design, synthesis, biological and structural evaluation of functionalized resveratrol analogues as inhibitors of quinone reductase 2
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Resveratrol (3,5,4′-trihydroxylstilbene) has been proposed to elicit a variety of positive health effects including protection against cancer and cardiovascular disease. The highest affinity target of resveratrol identified so far is the oxidoreductase enzyme quinone reductase 2 (QR2), which is believed to function in metabolic reduction and detoxification processes; however, evidence exists linking QR2 to the metabolic activation of quinones, which can lead to cell toxicity. Therefore, inhibition of QR2 by resveratrol may protect cells against reactive intermediates and eventually cancer. With the aim of identifying novel inhibitors of QR2, we designed, synthesized, and tested two generations of resveratrol analogue libraries for inhibition of QR2. In addition, X-ray crystal structures of six of the resveratrol analogues in the active site of QR2 were determined. Several novel inhibitors of QR2 were successfully identified as well as a compound that inhibits QR2 with a novel binding orientation.
- St. John, Sarah E.,Jensen, Katherine C.,Kang, Soosung,Chen, Yafang,Calamini, Barbara,Mesecar, Andrew D.,Lipton, Mark A.
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p. 6022 - 6037
(2013/09/23)
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- Copper-catalyzed cyanation of benzyl chlorides with non-toxic K 4[Fe(CN)6]
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Copper-based catalysts were firstly introduced into the cyanation of benzyl chlorides with non-toxic K4[Fe(CN)6]. The presented method avoids the use of extremely poisonous alkali cyanides and precious palladium catalysts. No other reagent apart from CuI, K4[Fe(CN) 6] and toluene was used in the cyanation, showing that the presented protocol is simple and practical. A series of benzyl chlorides were smoothly cyanated in up to 85% yield under the optimal conditions.
- Ren, Yunlai,Dong, Chuanhua,Zhao, Shuang,Sun, Yanpei,Wang, Jianji,Ma, Junying,Hou, Chaodong
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supporting information; experimental part
p. 2825 - 2827
(2012/07/17)
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- WATER-SOLUBLE AIE LUMINOGEN FOR MONITORING AND RETARDATION OF AMYLOID FIBRILLATION OF INSULIN
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The presently described subject matter is directed to a water-soluble conjugated polyene compound and the derivatives thereof that exhibit aggregation induced emission, as well as any water dispersible, fluorescent, polymeric microparticles, nanoparticles, and/or pharmaceutical composition comprising the water-soluble conjugated polyene compound and/or the derivatives thereof. Also provided are methods of making and using the compound, derivatives and particles of the presently described subject matter. The presently described water-soluble conjugated polyene compound are useful as bioprobes for the detection of biomacromolecules, in the manufacture of sensors, in monitoring and retarding formation of amyloid protein fibril in vitro and in vivo, and in developing anti-cancer drugs.
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- Synthesis of α-Aryl nitriles through palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates
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Worth its salt: The palladium-catalyzed decarboxylative coupling of the cyanoacetate salt as well as its mono- and disubstituted derivatives with aryl chlorides, bromides, and triflates is described (see scheme). This reaction is potentially useful for the preparation of a diverse array of α-aryl nitriles and has good functional group tolerance. S-Phos=2-(2,6- dimethoxybiphenyl)dicyclohexylphosphine), Xant-Phos=4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene. Copyright
- Shang, Rui,Ji, Dong-Sheng,Chu, Ling,Fu, Yao,Liu, Lei
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supporting information; experimental part
p. 4470 - 4474
(2011/06/24)
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- Fe(OTf)3-catalyzed reaction of benzylic acetates with organosilicon compounds
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Fe(OTf)3-catalyzed reaction of benzylic acetates with allyltrimethylsilane, azidotrimethylsilane, and cyanotrimethylsilane afforded the corresponding allylated, azido, and cyano products in high yields. 2-Trimethylsilyl-substituted benzofuran and indole worked well to furnish the benzyl-substituted benzofuran and indoles. Georg Thieme Verlag Stuttgart New York.
- Chan, Li Yan,Kim, Sundae,Chung, Wan Ting,Long, Chong,Kim, Sunggak
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experimental part
p. 415 - 419
(2011/04/22)
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- Design, synthesis and in vivo hypoglycemic activity of tetrazole-bearing N-glycosides as SGLT2 inhibitors
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Novel tetrazole-bearing N-glycosides have been designed and synthesized as SGLT2 inhibitors via a conventional protocol starting from substituted phenylacetic acids and two monosaccharides, D-glucose and D-galactose, and their hypoglycemic activity has been tested in vivo by mice oral glucose tolerance test (OGTT). Two compounds are found to be more potent than the positive control Dapagliflozin. The structure-activity relationship has also been investigated.
- Gao,Zhao,Liu,Shao,Wang,Tang,Wang
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experimental part
p. 1499 - 1508
(2011/02/22)
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- Microwave-promoted, one-pot conversion of alkoxymethylated protected alcohols into their corresponding nitriles, bromides, and iodides using [bmim][InCl4] as a green catalyst
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The Lewis acid room temperature ionic liquid, [bmim][InCl4], was found to be an efficient and green catalyst for the highly chemoselective and one-pot conversion of MOM- or EOM-ethers into their corresponding nitriles, bromides, and iodides under microwave irradiation. The procedures are simple, rapid, and high yielding. The catalyst exhibited a remarkable reactivity and is reusable.
- Mirjafari, Arsalan,Mohammadpoor-Baltork, Iraj,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Khosropour, Ahmad Reza
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supporting information; experimental part
p. 3274 - 3276
(2010/07/18)
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- H3PW12O40-[bmim][FeCl4]: A novel and green catalyst-medium system for microwave-promoted selective interconversion of alkoxymethyl ethers into their corresponding nitriles, bromides and iodides
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In the present work, the catalytic activity of 12-tungstophosphoric acid immobilized on [bmim][FeCl4] ionic liquid as a highly efficient and eco-friendly catalytic system for rapid and chemoselective direct conversion of MOM- or EOM-ethers into their corresponding nitriles, bromides and iodides under microwave irradiation is reported. In these reactions, the products are obtained in high yields. The catalyst exhibited remarkable reactivity and was reused several times.
- Mohammadpoor-Baltork, Iraj,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiolah,Mirjafari, Arsalan
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experimental part
p. 1468 - 1473
(2011/10/09)
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- Novel hybrids from lamellarin D and combretastatin A 4 as cytotoxic agents
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A new series of hybrids of lamellarin D and combretastatin A 4, 1,2-diphenyl-5,6-dihydropyrrolo [2,1-a] isoquinolines, were designed as cytotoxic agents based on principles of combination in medicinal chemistry and taking the parent compounds' different anti-proliferative mechanisms into consideration. Twenty-two novel hybrids were synthesized through a convenient route, with a key step of core pyrrole formation and evaluated for their anti-proliferative activities in vitro against K-562, A-549, SMMC-7721, SGC-7901 and HCT-116 cancer cell lines. The results showed that some hybrids had good anti-proliferative activities in low IC50 ranges.
- Shen, Li,Yang, Xiaochun,Yang, Bo,He, Qiaojun,Hu, Yongzhou
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scheme or table
p. 11 - 18
(2010/03/03)
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- Synthesis and biological evaluation of 3,4-diaryl-5-aminoisoxazole derivatives
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A series of cis-restricted 3,4-diaryl-5-aminoisoxazoles have been synthesized and evaluated for their biological activities. Among them, compound 11a and 13a displayed potent cytotoxic activities in vitro against five human cancer cell lines with IC50 values in the low micromolar range and two compounds inhibited tubulin polymerization with IC50 value of 1.8, and 2.1 μM, respectively, similar to that of CA-4. Compound 13a could arrest at the G2/M phase of the cell cycle at the concentration of 0.1 and 1.0 μM and induce apoptosis at 0.1-1.0 μM.
- Liu, Tao,Dong, Xiaowu,Xue, Na,Wu, Rui,He, Qiaojun,Yang, Bo,Hu, Yongzhou
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scheme or table
p. 6279 - 6285
(2011/02/24)
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- 8-(4-Methoxyphenyl)pyrazolo[1,5-a]-1,3,5-triazines: Selective and centrally active corticotropin-releasing factor receptor-1 (CRF1) antagonists
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This report describes the syntheses and structure-activity relationships of 8-(4-methoxyphenyl)pyrazolo-[1,5-a]-1,3,5-triazine corticotropin releasing factor receptor-1 (CRF1) receptor antagonists. CRF1 receptor antagonists may be potential anxiolytic or antidepressant drugs. This research culminated in the discovery of analogue 12-3, which is a potent, selective CRF1 antagonist (hCRF1 IC50 ) 4.7 ± 2.0 nM) with weak affinity for the CRF-binding protein and biogenic amine receptors. This compound also has a good pharmacokinetic profile in dogs. Analogue 12-3 is orally effective in two rat models of anxiety: the defensive withdrawal (situational anxiety) model and the elevated plus maze test. Analogue 12-3 has been advanced to clinical trials.
- Gilligan, Paul J.,He, Liqi,Clarke, Todd,Tivitmahaisoon, Parcharee,Lelas, Snjezana,Li, Yu-Wen,Heman, Karen,Fitzgerald, Lawrence,Miller, Keith,Zhang, Ge,Marshall, Anne,Krause, Carol,McElroy, John,Ward, Kathyrn,Shen, Helen,Wong, Harvey,Grossman, Scott,Nemeth, Gregory,Zaczek, Robert,Arneric, Stephen P.,Hartig, Paul,Robertson, David W.,Trainor, George
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scheme or table
p. 3073 - 3083
(2010/01/16)
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- Oxidative conversion of amines into their corresponding nitriles using o-iodoxybenzoic acid (IBX)/iodine: Selective oxidation of aminoalcohols to hydroxynitriles
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o-Iodoxybenzoic acid (IBX)/iodine in dimethyl sulfoxide at 65 °C oxidatively and efficiently converted various amines into the corresponding nitriles in good to excellent yields. Under the reaction conditions, amines were selectively oxidized to the nitrile in the presence of a primary hydroxy group within the same molecule. Thieme Stuttgart.
- Chiampanichayakul, Supanimit,Pohmakotr, Manat,Reutrakul, Vichai,Jaipetch, Thaworn,Kuhakarn, Chutima
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experimental part
p. 2045 - 2048
(2009/04/11)
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- A mild synthesis of nitriles by von Braun degradation of amides using triphenyl phosphite-halogen-based reagents
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A mild procedure for the synthesis of aromatic and aliphatic nitriles is disclosed. In the presence of bromotriphenoxyphosphonium bromide (TPPBr 2), N-alkyl and N,N-dialkyl amides undergo von Braun degradation to nitriles in good to excellent yields under the mildest conditions ever reported. The reaction proceeds via formation of an iminoyl bromide intermediate at -60°C, which subsequently dealkylate upon refluxing in chloroform or even at room temperature. In the case of N-tert-butyl, N-α-phenylethyl and N-benzhydryl amides, chlorotriphenoxyphosphonium chloride (TPPCl2) generated at -30°C was also effective. Georg Thieme Verlag Stuttgart.
- Vaccari, Daniele,Davoli, Paolo,Spaggiari, Alberto,Prati, Fabio
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experimental part
p. 1317 - 1320
(2009/04/06)
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- Controlled conversion of phenylacetic acids to phenylacetonitriles or benzonitriles using bis(2-methoxyethyl)aminosulfur trifluoride
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A mild, efficient, and practical method for the one-step synthesis of benzonitriles from phenylacetic acids using bis(2-methoxyethyl)aminosulfur trifluoride is described. The reaction was easily extended to the synthesis of the corresponding phenylacetonitriles by inclusion of triethylphosphine.
- Kangani, Cyrous O.,Day, Billy W.,Kelley, David E.
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p. 914 - 918
(2008/09/17)
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- An investigation of the reduction in aqueous acetonitrile of 4-methoxybenzenediazonium ion by the tetrakis(acetonitrile)Cu(i) cation catalysed by hydrogenphosphate dianion
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In aqueous acetonitrile containing a phosphate buffer, 4- methoxybenzenediazonium ion is reduced by one or more of the partially aquated cations derived from tetrakis(acetonitrile)Cu(i) cation in this medium. Investigation of the reaction mechanism indicates the rate determining step to be the association of the diazonium ion with the hydrogenphosphate dianion to give an adduct which then undergoes reduction by Cu(i). The reaction gives a range of products which have been identified and quantified by GC. One of these, 4-methoxyphenol was unexpected in the reducing conditions; its presence could be explained by the disproportionation of a 4-methoxyphenylcopper(ii) complex giving bis(4-methoxyphenyl)copper(iii) which reacts with water to produce the phenol and an equivalent amount of methoxybenzene. A scheme is proposed which accounts for all the observed products and computer modelling gives a satisfactory description of the distributions of the five major products as functions of the relative proportions of the reactants for dilute conditions and those where the reductant is in excess. When the diazonium ion is in excess, the behaviour of the model and the experimental reactant accountability suggest the occurrence of additional reactions which give products unobserved by GC. This journal is The Royal Society of Chemistry.
- Hanson, Peter,Taylor, Alec B.,Walton, Paul H.,Timms, Allan W.
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p. 679 - 698
(2008/03/27)
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- Mild palladium-catalyzed selective monoarylation of nitriles
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Two new palladium-catalyzed procedures for the arylation of nitriles under less basic conditions than previously reported have been developed. The selective monoarylation of acetonitrile and primary nitriles has been achieved using α-silyl nitriles in the presence of ZnF2. This procedure is compatible with a variety of functional groups, including cyano, keto, nitro, and ester groups, on the aryl bromide. The arylation of secondary nitriles occurred in high yield by conducting reactions with zinc cyanoalkyl reagents. These reaction conditions tolerated base-sensitive functional groups, such as ketones and esters. The combination of these two methods, one with a-silyl nitriles and one with zinc cyanoalkyl reagents, provides a catalytic route to a variety of benzylic nitriles, which have not only biological significance but utility as synthetic intermediates. The utility of these new coupling reactions has been demonstrated by a synthesis of verapamil, a clinically used drug for the treatment of heart disease, by a three-step route from commercial materials that allows convenient variation of the aryl group.
- Wu, Lingyun,Hartwig, John F.
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p. 15824 - 15832
(2007/10/03)
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- An insight of the reactions of amines with trichloroisocyanuric acid
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The reaction between amines or α-aminoacids with trichloroisocyanuric acid is studied under various conditions: N,N-dichloroamines, nitriles and ketones can be obtained from primary amines, while free aminoacids undergo oxidative decarboxylation to the corresponding nitrile of one less carbon atom.
- De Luca, Lidia,Giacomelli, Giampaolo
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p. 2180 - 2184
(2007/10/03)
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- Synthesis, selective aldose reductase inhibitory profile and antihyperglycaemic potential of certain parabanic acid derivatives
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Synthesis and aldose reductase inhibitory profile of certain parabanic acid derivatives 1a-p is described. Also, the antihyperglycaemic potential of these compounds was studied. The most active inhibitors in this series were compounds 1 g, 1p, and 1o which showed inhibitory activity, 36.6, 90 and 91% respectively, at concentration 1 × 10-4. Their IC50 were 2 × 10-6, 7.5 × 10-8 and 5 × 10-8, respectively. Compound 1o exhibited pronounced antihyperglycaemic effect.
- Nabil Aboul-Enein,El-Azzounya,Maklad,Attia,Wiese
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p. 329 - 350
(2007/10/03)
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- Design, synthesis and antiproliferative activity of tripentones: A new series of antitubulin agents
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Structure-activity relationship studies of a new series of tripentones (thieno[2,3-b]pyrrolizin-8-ones), led us to prepare several derivatives with antiproliferative activities. The most promising 3-(3-hydroxy-4-methoxyphenyl)thieno[2,3-b]pyrrolizin-8-one 20 (leukemia L1210, IC50 = 15 nM) was shown to be a potent inhibitor of tubulin polymerization.
- Lisowski, Vincent,Enguehard, Cecile,Lancelot, Jean-Charles,Caignard, Daniel-Henri,Lambel, Stephanie,Leonce, Stephane,Pierre, Alain,Atassi, Ghanem,Renard, Pierre,Rault, Sylvain
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p. 2205 - 2208
(2007/10/03)
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- High-temperature rearrangements of 2-acylisoxazol-5(2H)-ones and related oxazoles
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2-Acyl-3-arylisoxazol-5(2H)-ones give 2-alkyl(aryl)-4-aryloxazoles in good yields at 540°C under flash vacuum pyrolysis conditions, but at higher temperatures the expected oxazoles are accompanied by increasing amounts of isomeric 2,5-disubstituted oxazoles, as well as anilides and decomposition products of the 2,4-disubstituted oxazole. The rearrangement mechanisms have been studied by the use of 13C labelled substrates and p-substituted 3-arylisoxazolones. The 2,5-disubstituted oxazoles are considered to arise from 1H-azirines, and the anilides from the nitrone ketene isomer of the acylisoxazolone.
- Clark, Adrian D.,Ha, Uyen T.,Prager, Rolf H.,Smith, Jason A.
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p. 1029 - 1033
(2007/10/03)
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- Reactions of Charged Substrates. 8. The Nucleophilic Substitution Reactions of (4-Methoxybenzyl)dimethylsulfonium Chloride
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Displacement reactions on the title compound (1) occur only for nucleophiles with intermediate hardness. Nucleophiles that react display a range of mechanisms. 1 reacts with the neutral nucleophile pyridine-d5 through a mixed SN1/SN2 mechanism; salt added to control ionic strength affects the rate for the unimolecular process, but has no effect on the bimolecular rate constant. The mechanism of displacement by N3- and SO32- depends on the presence or absence of exogenous salt. At constant ionic strength, the mechanism is mixed SN1/SN2 over most of the range of [Nu]. With nucleophile only present, plots of kobsd vs [Nu] exhibit severe breaks that are not the result of salt effects. Analysis of rate constants and product ratios suggests that at low [Nu] reaction occurs simultaneously through concerted Hughes-Ingold SN2 and preassociation-concerted mechanisms. At high [Nu], displacement occurs only through the preassociation-concerted mechanism. Comparison of these results with data for gas-phase dissociation of benzyl dimethylsulfoniums and with solution results for benzyl pyridiniums suggests that the intrinsic stability of the intermediate does not necessarily determine the mechanism.
- Buckley, Neu,Oppenheimer, Norman J.
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p. 540 - 551
(2007/10/03)
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