- An expedient route to tricyanovinylindoles and indolylmaleimides fromo-alkynylanilines utilising DMSO as a one-carbon synthon
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A Pd(ii)/Cu(ii) catalysed domino synthesis of tricyanovinylindoles has been achieved using DMSO as a one-carbon synthon. The reaction proceedsviathe construction of 2-aryl-3-formyl indole followed by sequential addition of malononitrile and a CN resulting
- Chakraborty, Nikita,Dahiya, Anjali,Modi, Anju,Patel, Bhisma K.,Rakshit, Amitava
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supporting information
p. 6847 - 6857
(2021/08/20)
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- Copper-catalyzed synthesis and anticancer activity evaluation of indolo[1,2-a]quinoline derivatives
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A simple and effective one-pot synthesis of substituted indolo[1,2-a]quinolines has been developed. The desired products were obtained in up to 98% yield when substituted 2-methyindoles were treated with 2-iodobenzaldehyde in the presence of Cs2CO3, CuI and L-proline. Our mechanistic study confirmed that the reaction sequence involved an intermolecular Knoevenagel reaction followed by an intramolecular Ullmann-type coupling reaction. Moreover, some of the synthesized compounds were found to be active against human breast (MCF-7) and colorectal (HCT-116) cancer cells with IC50 values of 27.96 μM and in the range of 6.21–46.91 μM, respectively.
- Borwornpinyo, Suparerk,Chuanopparat, Nutthawat,Jearawuttanakul, Kedchin,Kanjanasirirat, Phongthon,Ngernmeesri, Paiboon,Rattanarat, Hassayaporn,Seemakhan, Sawinee,Thanetchaiyakup, Adisak
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- GaCl3-Catalyzed C-H Cyanation of Indoles with N-Cyanosuccinimide
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An efficient GaCl3-catalyzed direct cyanation of indoles and pyrroles using bench-stable electrophilic cyanating agent N-cyanosuccinimide was achieved and afforded 3-cyanoindoles and 2-cyanopyrroles in good yields and excellent regioselectivities. Notably, this protocol exhibited high reactivity for unprotected indoles and was applicable to a broad range of indole and pyrrole substrates.
- Wang, Xue,Makha, Mohamed,Chen, Shu-Wei,Zheng, Huaiji,Li, Yuehui
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p. 6199 - 6206
(2019/05/24)
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- Palladium-Catalyzed Late-Stage Direct Arene Cyanation
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Methods for direct benzonitrile synthesis are sparse, despite the versatility of cyano groups in organic synthesis and the importance of benzonitriles for the dye, agrochemical, and pharmaceutical industries. We report the first general late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance. The reaction is enabled by a dual-ligand combination of quinoxaline and an amino acid-derived ligand. The method is applicable to direct cyanation of several marketed small-molecule drugs, common pharmacophores, and organic dyes. Benzonitriles are some of the most versatile building blocks for organic synthesis, in particular in the pharmaceutical industry, but general methods to make them by direct C–H functionalization are unknown. In this issue of Chem, Ritter and coworkers describe a late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance, enabled by a palladium-dual-ligand catalyst system. The reaction may serve for the late-stage modification of drug candidates. Aryl nitriles constitute an important class of organic compounds that are widely found in natural products, pharmaceuticals, agricultural chemicals, dyes, and materials. Moreover, nitriles are versatile building blocks to access numerous other important molecular structure groups. However, no general method for direct aromatic C–H cyanation is known. All approaches to date require either an appropriate directing group or reactive electron-rich substrates, such as indoles, which limit their synthetic applications. Here we describe an undirected, palladium-catalyzed late-stage aryl C–H cyanation reaction for the synthesis of complex aryl nitriles that would otherwise be more challenging to produce. The wide substrate scope and good functional-group tolerance of this reaction provide direct and quick access to structural diversity for pharmaceutical and agrochemical development.
- Zhao, Da,Xu, Peng,Ritter, Tobias
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supporting information
p. 97 - 107
(2019/01/21)
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- One-pot synthesis of substituted indolo[1,2-a]quinolines under transition-metal-free conditions
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A simple and efficient one-pot synthesis of substituted indolo[1,2-a]quinolines under transition-metal-free conditions has been developed. When 2-fluorobenzaldehyde was treated with substituted 2-methylindoles in the presence of Cs2CO3, the desired products were typically obtained in good to excellent yields. This reaction sequence involves a nucleophilic aromatic substitution and a Knoevenagel condensation reaction. Our mechanistic investigation revealed that both reactions could proceed as an intermolecular reaction in the first step.
- Thanetchaiyakup, Adisak,Rattanarat, Hassayaporn,Chuanopparat, Nutthawat,Ngernmeesri, Paiboon
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p. 1014 - 1018
(2018/02/23)
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- Iodobenzene Dichloride/Zinc Chloride-Mediated Synthesis of N-Alkoxyindole-3-carbonitriles from 3-Alkoxyimino-2-arylalkylnitriles via Intramolecular Heterocyclization
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A series of N-alkoxyindole-3-carbonitriles were synthesized, under mild conditions, via intramolecular heterocyclization of the readily available 3-alkoxyimino-2-arylalkylnitriles mediated by iodobenzene dichloride/zinc chloride. The mechanism of the reaction proposes the formation of a key intermediate of nitrenium cation from a chlorination and dechlorination process facilitated by the hypervalent iodine reagent and Lewis acid respectively. (Figure presented.).
- Yun, Zhongxiang,Cheng, Ran,Sun, Jiyun,Zhang-Negrerie, Daisy,Du, Yunfei
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supporting information
p. 250 - 254
(2017/11/13)
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- A facile and efficient synthesis of 3-cyanoindoles by a simple palladium(II)-catalyzed C─H activation of indoles
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An efficient trans-PdCl2(NH2CH2COOH)2-catalyzed direct C3-cyanation of indole C─H bonds is described. Notably, free (N─H)-indoles reacted smoothly using the procedure, and the desired product 3-cyanoindoles were obtained in good to excellent yields.
- Chu, Hailiang,Guo, Mengping,Yi, Yanping,Wen, Yongju,Zhou, Lanjiang,Huang, Hongwei
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- Selective access to 3-cyano-1 H -indoles, 9 H -pyrimido[4,5- b ]indoles, or 9 H -Pyrido[2,3- b ]indoles through copper-catalyzed one-pot multicomponent cascade reactions
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Novel and selective synthetic approaches toward indole derivatives via copper-catalyzed one-pot multicomponent cascade reactions of 1-bromo-2-(2,2-dibromovinyl)benzenes with aldehydes and aqueous ammonia are presented. Intriguingly, the concentration of a
- Li, Bin,Guo, Shenghai,Zhang, Ju,Zhang, Xinying,Fan, Xuesen
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p. 5444 - 5456
(2015/06/16)
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- Cyanation of indoles with benzyl cyanide as the cyanide anion surrogate
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A copper-mediated direct cyanation of indoles with benzyl cyanide as the cyanide anion surrogate has been achieved. The cascade reaction furnished 3-cyanoindoles under mild reaction conditions in good to excellent yields with various functional groups tolerance.
- Zhang, Lianpeng,Wen, Qiaodong,Jin, Jisong,Wang, Chen,Lu, Ping,Wang, Yanguang
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p. 4236 - 4240
(2013/06/26)
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- Palladium-catalyzed C(sp2) - H cyanation using tertiary amine derived isocyanide as a cyano source
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An unprecedented palladium-catalyzed cyanation of aromatic C-H bonds by using tertiary amine derived isocyanide as a novel cyano source was developed. Cu(TFA)2 was used as a requisite stoichiometric oxidant. Mechanistic studies suggest that a tertiary carbon cation-based intermediate is involved following the C-N bond breakage.
- Peng, Jiangling,Zhao, Jiaji,Hu, Ziwei,Liang, Dongdong,Huang, Jinbo,Zhu, Qiang
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supporting information
p. 4966 - 4969,4
(2012/12/12)
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- Indole cyanation via CH bond activation under catalysis of Ru(III)-exchanged NaY zeolite (RuY) as a recyclable catalyst
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Selective 3-cyanation of indoles was achieved under heterogeneous catalysis of Ru(III)-exchanged NaY zeolite (RuY) as a recyclable catalyst, in combination with K4[Fe(CN)6] as a nontoxic, slow cyanide releasing agent. Under the aforementioned conditions, good yields of the desired products were obtained.
- Khorshidi, Alireza
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experimental part
p. 903 - 906
(2012/08/28)
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- Lewis acid catalyzed direct cyanation of indoles and pyrroles with N-cyano-N-phenyl-p-toluenesulfonamide (NCTS)
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BF3?OEt2-catalyzed direct cyanation of indoles and pyrroles using a less toxic, bench-stable, and easily handled electrophilic cyanating agent N-cyano-N-phenyl-para-toluenesulfonamide (NCTS) affords 3-cyanoindoles and 2-cyanopyrroles in good yields with excellent regioselectivity. The substrate scope is broad with respect to indoles and pyrroles.
- Yang, Yang,Zhang, Yan,Wang, Jianbo
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supporting information; experimental part
p. 5608 - 5611
(2011/12/03)
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- Exploring the oxidative cyclization of substituted N-aryl enamines: Pd-catalyzed formation of indoles from anilines
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The direct Pd-catalyzed oxidative coupling of two C-H-bonds within N-aryl-enamines 1 allows the efficient formation of differently substituted indoles 2. In this cross-dehydrogenative coupling, many different functional groups are tolerated and the starting material N-aryl-enamines 1 can be easily prepared in one step from commercially available anilines. In addition, the whole sequence can also be run in a one-pot fashion. Optimization data, mechanistic insight, substrate scope, and applications are reported in this full paper. Copyright
- Neumann, Julia J.,Rakshit, Souvik,Droege, Thomas,Wuertz, Sebastian,Glorius, Frank
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supporting information; experimental part
p. 7298 - 7303
(2011/08/21)
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- A base-modulated chemoselective synthesis of 3-cyanoindoles or 4-cyanoquinolines using a palladium-catalyzed N-heterocyclization
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A selective methodology for the synthesis of either 3-cyanoindoles or 4-cyanoquinolines via a base-modulated palladium-catalyzed reductive N-heterocyclization from a common 1-cyano-1-(2-nitrophenyl)-1-alkene precursor is described. The required starting materials were prepared either by a Kosugi-Migita-Stille coupling of 2-halo-1-nitrobenzenes with a tributyl(1-alkenyl)stannane or by a vicarious nucleophilic substitution (VNS) of nitrobenzenes followed by a Knoevenagel condensation with an aldehyde.
- Banini, Serge R.,Turner, Michael R.,Cummings, Matthew M.,S?derberg, Bj?rn C.G.
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p. 3603 - 3611
(2011/06/21)
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- Pd(OAc)2-catalyzed C-H activation of indoles: a facile synthesis of 3-cyanoindoles
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Indoles undergo smooth cyanation with CuCN in the presence of 20 mol % Pd(OAc)2 and 40 mol % CuBr2 in DMF to produce a wide range of the corresponding 3-cyanoindoles in good yields with high regioselectivity.
- Subba Reddy,Begum, Zubeda,Jayasudhan Reddy,Yadav
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experimental part
p. 3334 - 3336
(2010/07/06)
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- Palladium-catalyzed direct cyanation of indoles with K4[Fe(CN) 6]
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"Chemical equation presented" Direct cyanation of Indole derivatives has been achieved with nontoxic K4[Fe(CN)6] as cyanating agent through Pd-catalyzed C-H bond activation.
- Yan, Guobing,Kuang, Chunxiang,Zhang, Yan,Wang, Jianbo
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scheme or table
p. 1052 - 1055
(2010/06/13)
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- Propylphosphonic anhydride (T3P): A remarkably efficient reagent for the one-pot transformation of aromatic, heteroaromatic, and aliphatic aldehydes to nitriles
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Propylphosphonic anhydride has been demonstrated to be an efficient reagent for the transformation of aromatic, heteroaromatic, and aliphatic aldehydes to respective nitriles in excellent yields. This procedure offers simple and one-pot access to nitriles and highlights the synthetic utility of T3P as a versatile reagent in organic chemistry. Georg Thieme Verlag Stuttgart - New York.
- Augustine, John Kallikat,Atta, Rajendra Nath,Ramappa, Balakrishna Kolathur,Boodappa, Chandrakantha
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experimental part
p. 3378 - 3382
(2010/03/03)
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- Simple conversion of enamines to 2h-azirines and their rearrangements under thermal conditions
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A variety of substituted enamine derivatives were first found to be conveniently converted to the corresponding 2H-azirines mediated by phenyliodine (III) diacetate (PIDA). The formed 2-aryl-2W-azirines could be applied in the synthesis of indole-3-carbon
- Li, Xiaoxun,Du, Yunfei,Liang, Zhidan,Li, Xiangke,Pan, Yan,Zhao, Kang
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supporting information; experimental part
p. 2643 - 2646
(2009/10/02)
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- NITROGENATED HETEROCYCLIC COMPOUND AND PHARMACEUTICAL COMPOSITION COMPRISING THE SAME
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The present invention relates to novel compounds having a xanthine oxidase inhibitory effect and an uricosuric effect and pharmaceutical compositions comprising the same as an active ingredient. That is, the present invention relates nitrogen-containing heterocyclic compounds represented by the following general formula (I): wherein Y1 represents N or C(R4) ; Y2 represents N or C(R5) ; R4 and R5 independently represent an alkyl group, a hydrogen atom etc. ; one of R1 and R2 represents an optionally substituted aryl group, an alkoxygroup or an optionally substituted heterocyclic group; the other of R1 and R2 represents a haloalkyl group, a cyanogroup, ahalogenatometc.; and R3 represents a 5-tetrazolyl group or a carboxy group, and pharmaceutically acceptable salts thereof, and pharmaceutical compositions comprising the same as an active ingredient.
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Page/Page column 15; 19
(2008/12/06)
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- Rh(II)-catalyzed isomerization of 2-aryl-2H-azirines to 2,3-disubstituted indoles
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Various 2,3-disubstituted indoles are synthesized by Rh 2(OCOCF3)4-catalyzed isomerization of 2-aryl-2H-azirines. Copyright
- Chiba, Shunsuke,Hattori, Gaku,Narasaka, Koichi
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- A facile synthesis of 1-phenylsulfonyl-3-substituted-2-cyanoindoles, 1-phenylsulfonyl-2-methyl-3-cyanoindoles, and bifunctional 1- phenylsulfonylindoles
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A facile 'one-pot' introduction of the cyano group into the 2/3-position of indole has been developed from the corresponding aldehydes using anhydrous aluminum chloride and sodium azide. Georg Thieme Verlag Stuttgart.
- Jaisankar, Pichamuthu,Srinivasan
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p. 2413 - 2417
(2008/03/13)
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- Synihesis of 3-substituied indoles via a modified madeling reaction
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Anilides 4a-c,e-k, lla-d in which the amide function is benzylated, or silylated and having different electron-withdrawing groups (EWG) at the methyl methyl in the ortho position of the amide function, cyclize under the influence of potassium tert-butoxide to the corresponding indole derivatives 5a-c,e-k and 9a-d, respectively, under these conditions the chloroacetamides 4d,n and 11e are converted into the tetrahydroquinolines 6a,b and 12, respectively. Treatment of chloroacetamide 4m with KOt-Bu gave, in addition to starting material, indole 5m, tetrahydroquinoline 6c and 2(1H)-quinolinone 7. When 3-indolecarbonitrile 5a is treated with sodium in liquid amnonia debenzylation takes place, while after catalytic hydrogenation with 5% Pd/C the corresponding 2,3-dirnethylindole 8 is formed.
- Orlemans,Schreunder,Conti,Verboom,Reinhoudt
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p. 3817 - 3826
(2007/10/02)
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- A NOVEL SYNTHESIS OF 3-CYANOINDOLES AND A NEW ROUTE TO INDOLE-3-CARBOXYLIC ACID DERIVATIVES.
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2-Alkyl-3-cyanoindoles are obtained when 1-alkylmethyl-2-chloro-(or 2-phenylsulfonyl)-3-phenylsulfonylindoles are reacted with excess azide ion (90 deg C/DMF).The reaction is considered to occur by a fragmentation recombination process in which the Schiff
- Garcia, Josefina,Greenhouse, Robert,Muchowski, Joseph M.,Ruiz, Jose Antonio
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p. 1827 - 1830
(2007/10/02)
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- Cyanation using the Combined Reagent, Triphenylphosphine-Thiocyanogen (TPPT): A New General Route to Indole and Pyrrole Carbonitriles
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Various types of indoles, pyrroles, and enamines react with the combined reagent, Ph3P-(SCN)2 (TPPT) under mild conditions to give the corresponding cyanated compounds in high yields.The reaction mechanism of the cyanation is discussed.
- Tamura, Yasumitsu,Adachi, Masahiro,Kawasaki, Tomomi,Yasuda, Hitoshi,Kita, Yasuyuki
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p. 1132 - 1135
(2007/10/02)
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