cas 15861-24-2, 5-Cyanoindole | Articles data

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Visible light mediated selective oxidation of alcohols and oxidative dehydrogenation of N-heterocycles using scalable and reusable La-doped NiWO4nanoparticles
Visible light-mediated selective and efficient oxidation of various primary/secondary benzyl alcohols to aldehydes/ketones and oxidative dehydrogenation (ODH) of partially saturated heterocycles using a scalable and reusable heterogeneous photoredox catalyst in aqueous medium are described. A systematic study led to a selective synthesis of aldehydes under an argon atmosphere while the ODH of partially saturated heterocycles under an oxygen atmosphere resulted in very good to excellent yields. The methodology is atom economical and exhibits excellent tolerance towards various functional groups, and broad substrate scope. Furthermore, a one-pot procedure was developed for the sequential oxidation of benzyl alcohols and heteroaryl carbinols followed by the Pictet-Spengler cyclization and then aromatization to obtain the β-carbolines in high isolated yields. This methodology was found to be suitable for scale up and reusability. To the best of our knowledge, this is the first report on the oxidation of structurally diverse aryl carbinols and ODH of partially saturated N-heterocycles using a recyclable and heterogeneous photoredox catalyst under environmentally friendly conditions.
Abinaya, R.,Balasubramaniam, K. K.,Baskar, B.,Divya, P.,Mani Rahulan, K.,Rahman, Abdul,Sridhar, R.,Srinath, S.
p. 5990 - 6007
(2021/08/24)

Recyclable and Reusable Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O System for Cyanation of Aryl Chlorides with Potassium Ferrocyanide
Pd(OAc)2/XPhos–SO3Na in a mixture of poly(ethylene glycol) (PEG-400) and water is shown to be a highly efficient catalyst for the cyanation of aryl chlorides with potassium ferrocyanide. The reaction proceeded smoothly at 100 or 120?oC with K2CO3 or KOAc as base, delivering a variety of aromatic nitriles in good to excellent yields. The isolation of the crude products is facilely performed by extraction with cyclohexane and more importantly, both expensive Pd(OAc)2 and XPhos–SO3Na in PEG-400/H2O system could be easily recycled and reused at least six times without any apparent loss of catalytic efficiency. Graphical Abstract: Palladium-catalyzed cyanation of aryl chlorides with potassium ferrocyanide leading to aryl nitriles by using Pd(OAc)2/XPhos–SO3Na/PEG-400/H2O as a highly efficient and recyclable catalytic system is described.[Figure not available: see fulltext.]
Cai, Mingzhong,Huang, Bin,Liu, Rong,Xu, Caifeng
(2021/12/03)

Design, Synthesis, and Biological Evaluation of Novel 3-Aminomethylindole Derivatives as Potential Multifunctional Anti-Inflammatory and Neurotrophic Agents
The development of multifunctional molecules that are able to simultaneously interact with several pathological components has been considered as a solution to treat the complex pathologies of neurodegenerative diseases. Herein, a series of aminomethylindole derivatives were synthesized, and evaluation of their application for antineuroinflammation and promoting neurite outgrowth was disclosed. Our initial screening showed that most of the compounds potently inhibited lipopolysaccharide (LPS)-stimulated production of NO in microglial cells and potentiated the action of NGF to promote neurite outgrowth of PC12 cells. Interestingly, with outstanding NO/TNF-α production inhibition and neurite outgrowth-promoting activities, compounds 8c and 8g were capable of rescuing cells after injury by H2O2. Their antineuroinflammatory effects were associated with the downregulation of the LPS-induced expression of the inflammatory mediators inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2). Western blotting and immunofluorescence assay results indicated that the mechanism of their antineuroinflammatory actions involved suppression of the MAPK/NF-κB signal pathways. Further studies revealed that another important reason for the high comprehensive antineuroinflammatory activity was the anti-COX-2 capabilities of the compounds. All these results suggest that the potential biochemical multifunctional profiles of the aminomethylindole derivatives provide a new sight for the treatment of neurodegenerative diseases.
Wang, Wei-Wei,Liu, Ting,Lv, Yu-Meng,Zhang, Wu-Yang,Liu, Zhi-Gang,Gao, Jin-Ming,Li, Ding
p. 1593 - 1605
(2021/05/31)

Novel commercial scale synthetic approach for 5-cyanoindole: A potential intermediate for vilazodone hydrochloride, an antidepressant drug
Present work describes the synthesis of 5-cyanoindole, a common intermediate used in various synthetic route of the antidepressant vilazodone hydrochloride. The protocol is both robust and commercially viable, utilizing readily available and low-cost materials and the isomers are environmental friendly than previously reported routes through its evading use of cyanide reagents and heavy metals.
VENKATANARAYANA,NUCHU, RAVI,SHARATH BABU,GARREPALLI, GANGA SRAVANTHI,TANGALLAPALL, SUDHAKAR
p. 2460 - 2462
(2020/10/22)

Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
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
(2020/08/19)

Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
Herein, a Grubbs-catalyzed route for the synthesis of nitriles via the aerobic oxidation of primary amines is reported. This reaction accommodates a variety of substrates, including simple primary amines, sterically hindered β,β-disubstituted amines, allylamine, benzylamines, and α-amino esters. Reaction compatibility with various functionalities is also noted, particularly with alkenes, alkynes, halogens, esters, silyl ethers, and free hydroxyl groups. The nitriles were also synthesized via the oxidation of imines generated from aldehydes and NH4OAc in situ. (Figure presented.).
Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
supporting information
p. 3583 - 3588
(2020/08/05)

Decarboxylation of indole-3-carboxylic acids under metal-free conditions
Two reaction systems have been developed for the decarboxylation of indole-3-carboxylic acids. The decarboxylation can be achieved smoothly under K2CO3-catalyzed or acetonitrile-promoted basic conditions. It provided an efficient and simple method for the transformation of indole-3-carboxylic acids and the corresponding indoles were isolated with good to excellent yields. From the experimental facts, we put forward the possible reaction mechanism.
Chen, Xia,Zhou, Xiao-Yu
supporting information
p. 805 - 812
(2020/02/20)

Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
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
p. 1397 - 1405
(2020/02/04)

Electron Transfer Photoredox Catalysis: Development of a Photoactivated Reductive Desulfonylation of an Aza-Heteroaromatic Ring
Herein, we report a protocol for desulfonylation of aza-heteroaromatic rings via photoinduced electron transfer and hydrogen atom transfer. This general protocol has a wide substrate range and moderate to good yields. The utility of the method was demonstrated by the chemoselective desulfonylation of a molecule containing both an aliphatic and an aromatic sulfonamide. (Figure presented.).
Qiang-Liu,Liu, Yu-Xiu,Song, Hong-Jian,Wang, Qing-Min
supporting information
p. 3110 - 3115
(2020/07/04)

A NaH-promoted N-detosylation reaction of diverse p-toluenesulfonamides
A NaH-mediated detosylation reaction of various Ts-protected indoles, azaheterocycles, anilines and dibenzylamine was reported. The method features cheap reagent, convenient operations, mild reaction conditions and broad substrate scope. Moreover, this study revealed that the loading of NaH in tosylation reactions of nitrogen-containing compounds with NaH as a base in DMA or DMF should be controlled due to the possibility of adverse detosylation.
Sun, Wanwan,Chen, Xiaobei,Hu, Ying,Geng, Huihui,Jiang, Yuanrui,Zhou, Yuxin,Zhu, Wenjing,Hu, Min,Hu, Haohua,Wang, Xingyi,Wang, Xinli,Zhang, Shilei,Hu, Yanwei
supporting information

(2020/10/05)

Reusable, homogeneous water soluble photoredox catalyzed oxidative dehydrogenation of N-heterocycles in a biphasic system: Application to the synthesis of biologically active natural products
Herein, a simple and efficient method for the oxidative dehydrogenation (ODH) of tetrahydro-β-carbolines, indolines and tetrahydro-(iso)quinolines is described using a reusable, homogeneous cobalt-phthalocyanine photoredox catalyst in a biphasic medium. A biphasic system offers an advantage of easy separation of the product and an efficient reusability of the homogeneous photoredox catalyst. Also, the current system significantly helps to overcome the solubility issue of the substrate and catalyst at room temperature. Its potential applications to organic transformations are demonstrated by the synthesis of various biologically active N-heterocycles such as indoles, (iso)quinolines and β-carbolines and natural products such as eudistomin U, norharmane, and harmane and precursors to perlolyrine and flazin. Without isolation and purification, the catalyst solution can be reused up to 5 times with almost comparable reactivity. Furthermore, the efficiency of the reaction was demonstrated on a gram scale. To the best of our knowledge, this is the first report on ODH reactions using a non noble, reusable and homogeneous cobalt photoredox catalyst under environmentally friendly conditions.
Abinaya, R.,Baskar, B.,Mariappan, M.,Prasanth, Arun,Sridhar, R.,Srinath, S.
p. 2575 - 2587
(2020/05/13)

SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
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
p. 17288 - 17292
(2020/05/18)

Zn-catalyzed cyanation of aryl iodides
We report the first example of zinc-catalyzed cyanation of aryl iodides with formamide as the cyanogen source. The transformation was promoted by the bisphosphine Nixantphos ligand. Under optimized conditions, a variety of electron-donating and electron-withdrawing aryl iodides were converted into nitrile products in good to excellent yields. This approach is an exceedingly simple and benign method for the synthesis of aryl nitriles and is likely to proceed via a dinuclear Zn-concerted catalysis.
Zhao, Lulu,Dong, Yanan,Xia, Qiangqiang,Bai, Jianfei,Li, Yuehui
p. 6471 - 6477
(2020/06/08)

A carboxamide is the cyanogen source of aromatic nitrile to the preparation method of the (by machine translation)
The invention discloses a method for preparing aromatic nitrile, is under the action of the nickel catalyst, in order to carboxamide is the cyanogen source, and with various substituents haloarene coupled reactions, preparing aromatic nitrile. The reaction temperature is 100 - 160 °C, the reaction time is 6 - 24 hours. It overcomes the traditional aromatic nitrile of the synthesis method operation of complex steps, requires the use of a toxic, more expensive, functionalization of the cyanogen source as the reaction raw material and the like. Compared with the traditional method, this method is simple to use cheap, green non-toxic of the formamide is cyano sources; without the need of external dehydrating agent, formamide in the nickel catalyst of the catalytic dehydration at the same time, with a nickel catalyst in coordination with the halogenated aromatic hydrocyanation, more economic, high-efficiency, environmental protection; at the same time the method exhibits good substrate universality, to air, moisture, light are not sensitive, high yield, product separation and purification is simple, with wide application. (by machine translation)
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Paragraph 0015; 0016; 0017; 0018-0024; 0116; 0117-0121

(2019/05/08)

A 5 - cyano indole synthesis method (by machine translation)
The invention relates to a 5 - cyano indole synthesis method, through to indole as the starting material, with sodium bisulfite reaction, and then sequentially by acetylation, brominated, protection, [...] and de-protected to obtain 5 - cyano indole. The present invention provides a method of synthesis of the price of raw materials is low cost and easily, thereby reducing the production cost. At the same time the invention synthetic route is short, high yield, high chemical purity of the obtained product, all the reactions are not need special production equipment, and the produced intermediate and final products are not needs the column chromatography and crystallization purification. So the invention not only reduces production cost, convenient for the industrial scale production; and can provide the market with high purity products, obtain the good economic benefits. (by machine translation)
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Paragraph 0078-0083

(2019/11/13)

Potassium tert-Butoxide-Promoted Acceptorless Dehydrogenation of N-Heterocycles
Potassium tert-butoxide-promoted acceptorless dehydrogenation of N-heterocycles was efficiently realized for the generation of N-heteroarenes and hydrogen gas under transition-metal-free conditions. In the presence of KOtBu base, a variety of six- and five-membered N-heterocyclic compounds efficiently underwent acceptorless dehydrogenation to afford the corresponding N-heteroarenes and H2 gas in o-xylene at 140 °C. The present protocol provides a convenient route to aromatic nitrogen-containing compounds and H2 gas. (Figure presented.).
Liu, Tingting,Wu, Kaikai,Wang, Liandi,Yu, Zhengkun
supporting information
p. 3958 - 3964
(2019/08/01)

Ni-Mediated Generation of "cN" Unit from Formamide and Its Catalysis in the Cyanation Reactions
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
p. 3360 - 3365
(2019/03/26)

Nickel-catalyzed cyanation of aryl halides and triflates using acetonitrile: Via C-CN bond cleavage assisted by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine
We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)6](BF4)2, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (Si-Me4-DHP). Si-Me4-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C-CN bond cleavage.
Ueda, Yohei,Tsujimoto, Nagataka,Yurino, Taiga,Tsurugi, Hayato,Mashima, Kazushi
p. 994 - 999
(2019/02/03)

SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
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
p. 1484 - 1488
(2019/07/15)

Immobilized palladium nanoparticles on a cyclodextrin-polyurethane nanosponge (Pd-CD-PU-NS): An efficient catalyst for cyanation reaction in aqueous media
Immobilized palladium nanoparticles on a cyclodextrin-polyurethane nanosponge (Pd-CD-PU-NS) were found to be an efficient heterogeneous catalyst in the cyanation reaction of aryl halides in aqueous media. This catalyst system is containing palladium nanoparticles with a size of ～7 nm. Moreover, the CD-PU-NS support formed microsphere-shaped structures with a size of ～100–200 nm. The TEM images show that Pd nanoparticles were formed in near spherical shape morphology and were immobilized in the structure of the CD-PU-NS support. Under our optimized reaction conditions, aryl cyanides were obtained in high yields in the presence of the Pd-CD-PU-NS catalyst. Our results demonstrated that the Pd-CD-PU-NS catalyst is highly effective in the cyanation reaction in aqueous media. Furthermore, the catalyst could be simply extracted from the reaction mixture, providing an efficient methodology for the synthesis of aryl cyanides. The Pd-CD-PU-NS catalyst could be recycled four times with almost consistent catalytic efficiency.
Khajeh Dangolani, Soheila,Sharifat, Sara,Panahi, Farhad,Khalafi-Nezhad, Ali
supporting information
p. 256 - 265
(2019/06/07)

Nickel-Catalyzed Cyanation of Phenol Derivatives with Zn(CN)2 Involving C-O Bond Cleavage
An efficient nickel-catalyzed cyanation of aryl sulfonates, fluorosulfonates, and sulfamates with Zn(CN)2 was developed, which provides a facile access to the nitrile products in generally good to excellent yields. The reaction is accomplished by using NiII complex as the precatalyst and DMAP as the additive. The method also displays wide functional group compatibility; for example, keto, methoxy, N,N-dimethylamino, cyano, ester, and pyridyl groups are well-tolerated during the reaction process.
Gan, Yi,Wang, Gaonan,Xie, Xin,Liu, Yuanhong
p. 14036 - 14048
(2018/11/03)

Expanding the SAR of Nontoxic Antiplasmodial Indolyl-3-ethanone Ethers and Thioethers
Despite major strides in reducing Plasmodium falciparum infections, this parasite still accounts for roughly half a million annual deaths. This problem is compounded by the decreased efficacy of artemisinin combination therapies. Therefore, the development and optimisation of novel antimalarial chemotypes is critical. In this study, we describe our strategic approach to optimise a class of previously reported antimalarials, resulting in the discovery of 1-(5-chloro-1H-indol-3-yl)-2-[(4-cyanophenyl)thio]ethanone (13) and 1-(5-chloro-1H-indol-3-yl)-2-[(4-nitrophenyl)thio]ethanone (14), whose activity was equipotent to that of chloroquine against the P. falciparum 3D7 strain. Furthermore, these compounds were found to be nontoxic to HeLa cells as well as being non-haemolytic to uninfected red blood cells. Intriguingly, several of our most promising compounds were found to be less active against the isogenic NF54 strain, highlighting possible issues with long-term dependability of malarial strains. Finally compound 14 displayed similar activity against both the NF54 and K1 strains, suggesting that it inhibits a pathway that is uncompromised by K1 resistance.
Lunga, Mayibongwe J.,Chisango, Ruramai L.,Weyers, Carli,Isaacs, Michelle,Taylor, Dale,Edkins, Adrienne L.,Khanye, Setshaba D.,Hoppe, Heinrich C.,Veale, Clinton G. L.
p. 1353 - 1362
(2018/07/13)

Catalytic Cyanation Using CO2 and NH3
Li and co-workers describe the catalytic cyanation of organic halides with CO2 and NH3. In the presence of Cu2O/DABCO as the catalyst, a variety of aromatic bromides and iodides were transformed to the desired nitrile products with broad functional-group tolerance. Both 13C- and/or 15N-labeled nitriles were obtained conveniently with appropriately isotope-labeled CO2 and NH3. Construction of functionalized chemical compounds from small molecules in a highly selective and efficient manner is crucial for sustainable development. The chemical-based manufacturing sector of the future should aim to produce chemicals from very simple and abundant resources, just as nature uses CO2 and N2 to generate sugars, amino acids, and so forth. In practice, however, the utilization of CO2 for the generation of industrial products, such as drugs and related intermediates, still remains a major challenge. Here, we describe the facile cyanide-free production of high-value nitriles with CO2 and NH3 as the sole sources of carbon and nitrogen, respectively. This practical and catalytic methodology provides a unique strategy for the utilization of small molecules for sustainable and cost-effective applications. Selective cyanation of aryl halides was achieved with CO2 and NH3 as the only sources of carbon and nitrogen, respectively. In the presence of Cu catalysts under low pressure (3 atm), a variety of aromatic iodides and bromides were transformed to the desired nitrile products without the use of toxic metal cyanides. Notably, olefins, esters, amides, alcohols, and amino groups were tolerated. Mechanistic studies suggest that Cu(III)-aryl insertion by isocyanate intermediates is involved. [13C,15N]-labeled nitriles were conveniently accessible from the respective isotope-labeled CO2 and NH3 via this methodology.
Wang, Hua,Dong, Yanan,Zheng, Chaonan,Sandoval, Christian A.,Wang, Xue,Makha, Mohamed,Li, Yuehui
supporting information
p. 2883 - 2893
(2019/01/05)

Cyaniding method for preparing nitrile compound
The invention provides a cyaniding method for preparing a nitrile compound. Organic halide or pseudohalide, CO2 and NH3 which are low in price and are easily obtained and a reducing agent react, a selective cyaniding reaction is conducted in the presence of a transition metal catalyst, and the target product namely organic the nitrile compound is obtained. According to the cyaniding method for preparing the nitrile compound, a new reaction route is used, through a CO2 and NH3 reaction of metal catalysis, dehalogenation cyaniding or quasi halide cyaniding of halide or pseudohalide is directly achieved through a one-pot method, the problem is solved that a traditional cyanation reaction needs equivalent toxic cyanide, a new direct and convenient method for preparing isotope-labeled nitrile compounds is provided at the same time, and the method can be applied to medicine, tracing, biology and medicine research and development.
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Paragraph 0101-0103

(2018/05/30)

Nickel-Catalyzed Deoxycyanation of Activated Phenols via Cyanurate Intermediates with Zn(CN)2: A Route to Aryl Nitriles
A novel, and efficient nickel-catalyzed deoxycyanation of phenolic compounds using relatively nontoxic Zn(CN)2 as the cyanide source was developed. The reaction of C-O bond activated phenolic compounds by 2,4,6-trichloro-1,3,5-triazine with Zn(CN)2 in the presence of a nickel precatalyst afforded the aromatic nitriles in good to excellent yields.
Heravi, Majid M.,Panahi, Farhad,Iranpoor, Nasser
supporting information
p. 2753 - 2756
(2018/05/22)

Preparation method of aromatic nitrile compound or heteroaromatic nitrile compound
The invention discloses a preparation method of an aromatic nitrile compound or a heteroaromatic nitrile compound. The preparation method comprises: under the protection of an inert gas, in a solvent,under the actions of a nickel catalyst, a ligand, metal zinc and an additive, carrying out a reaction on a cyanation reagent and halogenated aromatic hydrocarbon or halogenated heteroaromatic hydrocarbon. According to the present invention, by using the inexpensive and easily-available nickel catalyst and the ligand, the halogenated aromatic hydrocarbon or halogenated heteroaromatic hydrocarbon,especially the chlorinated aromatic hydrocarbon or chlorinated heteroaromatic hydrocarbon with characteristics of low price, easy obtaining and low reaction activity can mildly and efficiently react with the cyanation reagent with low toxicity to prepare the aromatic nitrile compound or heteroaromatic nitrile compound; and the preparation method has advantages of simple operation, mildness, high efficiency and the like, and further has characteristics of good functional group compatibility, good universality of substrate and the like.
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Paragraph 0043; 0045; 0207-0209

(2018/11/03)

Photoinduced Copper(I)-Catalyzed Cyanation of Aromatic Halides at Room Temperature
The first photoinduced copper(I)-catalyzed cyanation of aromatic halides at room temperature has been developed. The sp2 cyanation reaction exhibits outstanding tolerance to functional groups including primary amines and carboxylic acids, and chemoselectivity to SN2-reactive alkyl chlorides. Mechanistic investigations indicate that the reaction occurs via a single-electron transfer (SET) between the aryl halide and an excited copper(I) cyanide catalytic intermediate. (Figure presented.).
Kim, Kicheol,Hong, Soon Hyeok
supporting information
p. 2345 - 2351
(2017/07/22)

General and Mild Nickel-Catalyzed Cyanation of Aryl/Heteroaryl Chlorides with Zn(CN)2: Key Roles of DMAP
A new and general nickel-catalyzed cyanation of hetero(aryl) chlorides using less toxic Zn(CN)2 as the cyanide source has been developed. The reaction relies on the use of inexpensive NiCl2·6H2O/dppf/Zn as the catalytic system and DMAP as the additive, allowing the cyanation to occur under mild reaction conditions (50-80 °C) with wide functional group tolerance. DMAP was found to be crucial for successful transformation, and the reaction likely proceeds via a Ni(0)/Ni(II) catalysis based on mechanistic studies. The method was also successfully extended to aryl bromides and aryl iodides.
Zhang, Xingjie,Xia, Aiyou,Chen, Haoyi,Liu, Yuanhong
supporting information
p. 2118 - 2121
(2017/04/27)

Synthesis of nitriles from amines using nanoscale Co3O4-based catalysts via sustainable aerobic oxidation
The selective oxidation of amines for the benign synthesis of nitriles under mild conditions is described. Key to success for this transformation is the application of reusable cobalt oxide-based nanocatalysts. The resulting nitriles constitute key precursors and central intermediates in organic synthesis.
Natte, Kishore,Jagadeesh, Rajenahally V.,Sharif, Muhammad,Neumann, Helfried,Beller, Matthias
supporting information
p. 3356 - 3359
(2016/04/09)

Synthesis of aryl nitriles by palladium-assisted cyanation of aryl iodides using tert-butyl isocyanide as cyano source
Abstract A palladium-catalyzed synthesis of aryl nitriles by the cyanation of aryl iodides with tert-butyl isocyanide as cyano source has been developed. This novel and efficient method avoids the use of toxic cyanides. The reaction is easy-to-handle and shows good functional group compatibility.
Jiang, Xiao,Wang, Jin-Mei,Zhang, Ying,Chen, Zhong,Zhu, Yong-Ming,Ji, Shun-Jun
p. 4883 - 4887
(2015/08/03)

"Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2O3)-based catalysts applying molecular oxygen.
Jagadeesh, Rajenahally V.,Junge, Henrik,Beller, Matthias
p. 92 - 96
(2015/02/19)

Mild palladium-catalyzed cyanation of (hetero)aryl halides and triflates in aqueous media
A mild, efficient, and low-temperature palladium-catalyzed cyanation of (hetero)aryl halides and triflates is reported. Previous palladium-catalyzed cyanations of (hetero)aryl halides have required higher temperatures to achieve good catalytic activity. This current reaction allows the cyanation of a general scope of (hetero)aryl halides and triflates at 2-5 mol % catalyst loadings with temperatures ranging from rt to 40 °C. This mild method was applied to the synthesis of lersivirine, a reverse transcriptase inhibitor.
Cohen, Daniel T.,Buchwald, Stephen L.
supporting information
p. 202 - 205
(2015/01/30)

One-pot tandem synthesis of 2,3-unsubstituted indoles, an improved Leimgruber-Batchoindole synthesis
A concise, fast and efficient one-pot methodology has been developed for preparing 2,3-unsubstituted indoles from 2-nitrotoluenes and dimethylformamide dimethyl acetal. Compared with the classical Leimgruber-Batcho reaction, such a one-pot process simplified the operation procedures, generated less by-products and chemical residues, and resulted in higher overall yields in a shorter reaction time.
Chen, Jinchun,Zhang, Zhikai,Liu, Sujing,Yang, Cuiyun,Xia, Chuanhai
p. 4672 - 4675
(2014/01/17)

Copper catalyzed nitrile synthesis from aryl halides using formamide as a nitrile source
A copper iodide/triphenyl phosphine catalyzed simple and efficient protocol has been developed for cyanide free cyanation of aryl halide using formamide as a cyanide source. The reaction works well to furnish aryl nitriles using an inexpensive and easily available copper catalyst with triphenyl phosphine and phosphorus oxychloride. Under the optimized reaction conditions, a variety of electron-donating and electron-withdrawing aryl halides were efficiently converted into the respective nitriles in moderate to excellent yields. This journal is the Partner Organisations 2014.
Khemnar, Ashok B.,Bhanage, Bhalchandra M.
p. 13405 - 13408
(2014/04/03)

Cyanation of aryl chlorides using a microwave-assisted, copper-catalyzed concurrent tandem catalysis methodology
A microwave-assisted, copper-catalyzed concurrent tandem catalytic (CTC) methodology has been developed for the cyanation of aryl chlorides, where the aryl chloride is first converted to an aryl iodide via halogen exchange and the aryl iodide is subsequently transformed to the aryl nitrile. A variety of aryl chlorides were converted to aryl nitriles in 44-97% yield using 20 mol % of CuI, 40 mol % of N,N'-cyclohexane-1,2-diamine, and 1.2 equiv of KCN in acetonitrile at 200 C after 1-2 h. The same copper/ligand system served as a multifunctional catalyst for both steps of the concurrent catalytic process. Unlike our previously reported CTC hydrodehalogenation of aryl chlorides, CTC cyanation was catalytic in iodide. Kinetic simulations of the proposed CTC mechanism were consistent with experimental results and stipulate the relative reaction rates of the two catalytic cycles necessary to achieve reasonable yields of product. This article not subject to U.S. Copyright. Published 2013 by the American Chemical Society.
Coughlin, Mary M.,Kelly, Colin K.,Lin, Shirley,Macarthur, Amy H. Roy
supporting information
p. 3537 - 3543
(2013/07/26)

Conversion of aldoximes into nitriles and amides under mild conditions
A series of Pd(en)X2 salts were used as catalysts for the conversion of aldoximes into nitriles and amides. Highlights of this protocol include the use of inexpensive polar solvents, including water, and moderate reaction temperatures. A high degree of selectivity in the reaction outcome was observed when using aliphatic vs. aromatic/conjugated aldoximes. The Royal Society of Chemistry 2013.
Tambara, Koujiro,Pantos, G. Dan
p. 2466 - 2472
(2013/06/05)

Efficient palladium-catalyzed cyanation of aryl/heteroaryl bromides with K4[Fe(CN)6] in t-BuOH-H2O using tris(2-morpholinophenyl)phosphine as a ligand
A practical method for the synthesis of various aryl/heteroaryl nitriles using non-toxic K4[Fe(CN)6] as the cyanide source is described. The cyanation of aryl/heteroaryl bromides with K4[Fe(CN) 6] proceeded smoothly in the presence of a Pd/tris(2- morpholinophenyl)phosphine (L5) catalyst under mild conditions. The corresponding aryl/heteroaryl nitriles were produced in good to excellent yields. The Royal Society of Chemistry 2013.
Zou, Tao,Feng, Xiujuan,Liu, Hesong,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
p. 20379 - 20384
(2013/11/06)

Rhodium catalyzed cyanide-free cyanation of aryl halide by using formamide as a cyanide source
This work reports rhodium-xantphos as a new catalytic system for cyanide-free cyanation of aryl halides to aryl nitriles. The reaction takes place in the presence of phosphorous oxychloride as an acid and formamide as a cyanide source cum solvent. The developed protocol avoids the use of highly toxic metal cyanides. This methodology is a simple, single step reaction involving formamide as a safe and nontoxic source of cyanation. A variety of aryl iodides/bromides were well tolerated under optimized reaction conditions providing moderate to excellent yield of corresponding cyanides.
Khemnar, Ashok B.,Sawant, Dinesh N.,Bhanage, Bhalchandra M.
p. 2682 - 2684
(2013/06/26)

Formation of indoles, dihydroisoquinolines, and dihydroquinolines by ruthenium-catalyzed heterocyclizations
Indoles, dihydroisoquinolines, and dihydroquinolines were efficiently prepared by ruthenium-catalyzed heterocyclizations of aromatic homo- and bis-homopropargyl amines/amides in the presence of an amine/ammonium base-acid pair. These regioselective 5-endo and 6-endo cyclizations most probably occur by nucleophilic trapping of key ruthenium-vinylidene intermediates. Georg Thieme Verlag Stuttgart · New York.
Varela-Fernández, Alejandro,Varela, Jesús A.,Saá, Carlos
p. 3285 - 3295
(2013/01/15)

Pd-grafted periodic mesoporous organosilica: An efficient heterogeneous catalyst for Hiyama and Sonogashira couplings, and cyanation reactions
The high surface area of 2D-hexagonal periodic mesoporous organosilica (PMO) containing a phloroglucinol-diimine moiety inside the pore wall has been utilized for grafting Pd(ii) at the surface of the mesopores. This Pd-containing PMO material (Pd-LHMS-3) shows excellent catalytic activity in fluoride-free Hiyama cross-coupling reactions in water at alkaline pH conditions. Sonogashira cross-couplings between terminal alkynes and aryl halides take place in the presence of water and hexamine as base in the absence of any Cu co-catalyst. Cyanation of aryl halides is equally promoted with K4[Fe(CN) 6] as the cyanide source (in the absence of poisonous KCN, NaCN or Zn(CN)2) over Pd-LHMS-3. Excellent yield of the products, reusability and the facile work-up could make this Pd-grafted PMO material a unique catalyst for the synthesis of substituted benzonitriles, unsymmetrical biphenyls and di-substituted alkynes under environmentally benign reaction conditions. Further good yield of products and no evidence of leached Pd from the catalyst surface during the reaction and its smooth recovery confirm the true heterogeneity in these catalytic reactions.
Modak, Arindam,Mondal, John,Bhaumik, Asim
p. 2840 - 2855
(2012/11/07)

An expedient Pd/DBU mediated cyanation of aryl/heteroaryl bromides with K4[Fe(CN)6]
A practical Pd(PPh3)4/DBU catalytic system for the synthesis of pharmaceutically relevant aminopyridine nitrile intermediates, as well as a variety of other aryl nitriles using non-toxic K4[Fe(CN) 6] has been developed. The key features of our new protocol for cyanation lie in that the reaction can be carried out with readily available Pd(PPh3)4 under mild and green conditions, even without the assistance of other ligands. The Royal Society of Chemistry 2012.
Zhang, Dengyou,Sun, Haifeng,Zhang, Lei,Zhou, Yu,Li, Chunpu,Jiang, Hualiang,Chen, Kaixian,Liu, Hong
supporting information; experimental part
p. 2909 - 2911
(2012/03/27)

Ruthenium-catalyzed cycloisomerization of aromatic homo- and bis-homopropargylic amines/amides: Formation of indoles, dihydroisoquinolines and dihydroquinolines
Ruthenium-catalyzed cycloisomerizations of aromatic homo- and bis-homopropargylic amines/amides efficiently afford indoles, dihydroisoquinolines and dihydroquinolines. These processes were regioselective (5- and 6-endo cyclizations) on using key Ru vinylidene intermediates. The presence of an amine/ammonium base-acid pair increased the rate of cyclization and facilitated the catalytic turnover. Copyright
Varela-Fernandez, Alejandro,Varela, Jesus A.,Saa, Carlos
supporting information; experimental part
p. 1933 - 1937
(2011/10/08)

Cyanides-free cyanation of aryl halides using formamide
A novel method for cyanation of aryl halides using formamide as a non-toxic cyanide source is reported. It is a single-step, solvent-free method wherein formamide itself acts as solvent as well as source of cyanide in the presence of phosphorus oxychloride and palladium acetate/xantphos catalyst. Aryl iodides as well as aryl bromides provided moderate to excellent yields of up to 93%. Copyright
Sawant, Dinesh N.,Wagh, Yogesh S.,Tambade, Pawan J.,Bhatte, Kushal D.,Bhanage, Bhalchandra M.
experimental part
p. 781 - 787
(2011/06/11)

A mild and efficient palladium-catalyzed cyanation of aryl chlorides with K4[Fe(CN)6]
An efficient palladium-catalyzed cyanation of aryl chlorides is established. In the presence of a highly effective Pd/CM-phos catalyst, cyanation of aryl chlorides proceeds at 70 °C in general, which is the mildest reaction temperature achieved so far for this process. Common functional groups such as keto, aldehyde, ester, nitrile and-NH2, and heterocyclic coupling partners including N-H indoles are well tolerated. Moreover, a sterically hindered nonactivated ortho,ortho-disubstituted electrophile is shown to be a feasible coupling partner in cyanation.
Yeung, Pui Yee,So, Chau Ming,Lau, Chak Po,Kwong, Fuk Yee
supporting information; experimental part
p. 648 - 651
(2011/04/15)

Development of Pd/C-catalyzed cyanation of Aryl halides
A practical method for palladium-catalyzed cyanation of aryl halides using Pd/C is described. The new method can be applied to a variety of aryl bromide and active aryl chloride substrates to effect efficient conversions. The process features many advantages over existing cyanation conditions and the practical utility of the process has been demonstrated on scale.
Yu, Hannah,Richey, Rachel N.,Miller, William D.,Xu, Jiansheng,May, Scott A.
supporting information; experimental part
p. 665 - 668
(2011/03/19)

Indolyne experimental and computational studies: Synthetic applications and origins of selectivities of nucleophilic additions
Efficient syntheses of 4,5-, 5,6-, and 6,7-indolyne precursors beginning from commercially available hydroxyindole derivatives are reported. The synthetic routes are versatile and allow access to indolyne precursors that remain unsubstituted on the pyrrole ring. Indolynes can be generated under mild fluoride-mediated conditions, trapped by a variety of nucleophilic reagents, and used to access a number of novel substituted indoles. Nucleophilic addition reactions to indolynes proceed with varying degrees of regioselectivity; distortion energies control regioselectivity and provide a simple model to predict the regioselectivity in the nucleophilic additions to indolynes and other unsymmetrical arynes. This model has led to the design of a substituted 4,5-indolyne that exhibits enhanced nucleophilic regioselectivity.
Im, G-Yoon J.,Bronner, Sarah M.,Goetz, Adam E.,Paton, Robert S.,Cheong, Paul H.-Y.,Houk,Garg, Neil K.
supporting information; experimental part
p. 17933 - 17944
(2011/02/26)

S1P RECEPTORS MODULATORS
The invention relates to novel compounds that have S1P receptor modulating activity and, preferably, apoptotic activity and/or anti proliferative activity against cancer cells and other cell types. Further, the invention relates to a pharmaceutical comprising at least one compound of the invention for the treatment of diseases and/or conditions caused by or associated with inappropriate S1P receptor modulating activity or expression, for example, cancer. A further aspect of the invention relates to the use of a pharmaceutical comprising at least one compound of the invention for the manufacture of a medicament for the treatment of diseases and/or conditions caused by or associated with inappropriate S1P receptor modulating activity or expression such as cancer.
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(2010/04/30)

A mild and efficient palladium-catalyzed cyanation of aryl mesylates in water or tBuOH/water
Cool and compatible: Aryl mesylates and tosylates underwent palladium-catalyzed cyanation under mild, aqueous conditions at 65-80°C (see scheme). In many cases, water could be used as the reaction medium without a cosolvent, and a variety of substituents R, such as keto, aldehyde, ester, free amine, and nitrile groups, remained intact during the transformation. Cy=cyclohexyl, Ms=methanesulfonyl, Ts=p-toluenesulfonyl.
Yeung, Pui Yee,So, Chau Ming,Lau, Chak Po,Kwong, Fuk Yee
supporting information; experimental part
p. 8918 - 8922
(2011/02/24)

OXADIAZOLE FUSED HETEROCYCLIC DERIVATIVES USEFUL FOR THE TREATMENT OF MULTIPLE SCLEROSIS
The invention provides compounds of Formula (I) for the treatment of multiple sclerosis and other diseases.
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Page/Page column 54

(2010/08/05)

Design, synthesis and anti-proliferative studies of a novel series of indirubin derivatives
A series of novel derivatives of indirubin were synthesized and evaluated for their anti-proliferative activity against human cancer cell lines of SGC7901, A549, HL-60, SK-BR-3 and HCT116. Most of the compounds displayed more potent activity than Sunitinib. In addition, the derivatives showed improved water solubility, which may be favorable to their pharmacokinetic performances.
Wang, Tian Cai,Wei, Ju Zhi,Guo, Chuan Sheng,Zhang, Hui Bin,Fan, Hou Xing
scheme or table
p. 1407 - 1410
(2011/10/09)