- Nickel-catalyzed cyclization of 1,7-enynes for the selective synthesis of dihydrocyclobuta[c]quinolin-3-ones and benzo[b]azocin-2-ones
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We herein described a nickel-catalyzed cyclization ofN-(o-ethynylaryl)acrylamides for the selective synthesis of dihydrocyclobuta[c]quinolin-3-ones and benzo[b]azocin-2-ones. The two varied products could be easily obtained by tuning the reaction temperature. This reaction features easy temperature-control, high efficiency, and gram-scale synthesis.
- Cai, Yun,Chen, Fener,Hu, Yuanyuan,Jin, Hongwei,Li, Qiao,Liu, Yunkui,Zhou, Bingwei
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supporting information
p. 11657 - 11660
(2021/11/12)
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- Copper-Catalyzed Aerobic Oxidative Cyclization of 2-Alkynylanilines with Nitrosoarenes: Synthesis of Organic Solid Mechanoluminescence Compounds of 4-Oxo-4 H-cinnolin-2-ium-1-ide
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An efficient Cu(I)/DMAP/air system for the one-pot synthesis of 4-oxo-4H-cinnolin-2-ium-1-ides, which are often difficult to prepare by traditional routes from substituted 2-alkynylanilines and nitrosoarenes, was developed. These 4-oxo-4H-cinnolin-2-ium-1-ides have practical applications as mechanoluminescent materials. Preliminary mechanistic experiments were performed, and a plausible mechanism for this tandem process is proposed. The use of an inexpensive copper catalyst and molecular oxygen as the oxygen source and the oxidant make this an attractive green protocol with potential synthetic applications.
- Fang, Xiaolan,Cao, Ji,Ding, Weijie,Jin, Huile,Yu, Xiaochun,Wang, Shun
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supporting information
p. 1228 - 1233
(2021/02/20)
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- Chiral Br?nsted Acid from Chiral Phosphoric Acid Boron Complex and Water: Asymmetric Reduction of Indoles
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A new chiral Br?nsted acid, generated in situ from a chiral phosphoric acid boron (CPAB) complex and water, was successfully applied to asymmetric indole reduction. This “designer acid catalyst”, which is more acidic than TsOH as suggested by DFT calculations, allows the unprecedented direct asymmetric reduction of C2-aryl-substituted N-unprotected indoles and features good to excellent enantioselectivities with broad functional group tolerance. DFT calculations and mechanistic experiments indicates that this reaction undergoes C3-protonation and hydride-transfer processes. Besides, bulky C2-alkyl-substituted N-unprotected indoles are also suitable for this system.
- Yang, Kai,Lou, Yixian,Wang, Chenglan,Qi, Liang-Wen,Fang, Tongchang,Zhang, Feng,Xu, Hetao,Zhou, Lu,Li, Wangyang,Zhang, Guan,Yu, Peiyuan,Song, Qiuling
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supporting information
p. 3294 - 3299
(2020/01/21)
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- Cobalt-Catalyzed Enantioselective Hydroboration/Cyclization of 1,7-Enynes: Asymmetric Synthesis of Chiral Quinolinones Containing Quaternary Stereogenic Centers
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An asymmetric cobalt-catalyzed hydroboration/cyclization of 1,7-enynes to synthesize chiral six-membered N-heterocyclic compounds was developed. A variety of aniline-tethered 1,7-enynes react with pinacolborane to afford the corresponding chiral boryl-fun
- Wu, Caizhi,Liao, Jiayu,Ge, Shaozhong
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supporting information
p. 8882 - 8886
(2019/06/13)
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- Copper-catalyzed trifluoromethylazidation and rearrangement of aniline-linked 1,7-enynes: Access to CF3-substituted azaspirocyclic dihydroquinolin-2-ones and furoindolines
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A set of reactions involving copper-catalyzed trifluoromethylazidation and then rearrangement of aniline-linked 1,7-enynes with the relatively poorly reactive Togni reagent I and TMSN3 was developed, and provided facile access to structurally d
- Yu, Liu-Zhu,Wei, Yin,Shi, Min
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supporting information
p. 8980 - 8983
(2017/08/15)
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- Stereoselective Synthesis of Methylene Oxindoles via Palladium(II)-Catalyzed Intramolecular Cross-Coupling of Carbamoyl Chlorides
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We report a highly robust, general and stereoselective method for the synthesis of 3-(chloromethylene)oxindoles from alkyne-tethered carbamoyl chlorides using PdCl2(PhCN)2 as the catalyst. The transformation involves a stereo- and regioselective chloropalladation of an internal alkyne to generate a nucleophilic vinyl PdII species, which then undergoes an intramolecular cross-coupling with a carbamoyl chloride. The reaction proceeds under mild conditions, is insensitive to the presence of moisture and air, and is readily scalable. The products obtained from this reaction are formed with >95:5 Z:E selectivity in nearly all cases and can be used to access biologically relevant oxindole cores. Through combined experimental and computational studies, we provide insight into stereo- and regioselectivity of the chloropalladation step, as well as the mechanism for the C-C bond forming process. Calculations provide support for a mechanism involving oxidative addition into the carbamoyl chloride bond to generate a high valent PdIV species, which then undergoes facile C-C reductive elimination to form the final product. Overall, the transformation constitutes a formal PdII-catalyzed intramolecular alkyne chlorocarbamoylation reaction.
- Le, Christine M.,Sperger, Theresa,Fu, Rui,Hou, Xiao,Lim, Yong Hwan,Schoenebeck, Franziska,Lautens, Mark
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supporting information
p. 14441 - 14448
(2016/11/13)
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- Expedient Access to Unsymmetrical Diarylindolylmethanes through Palladium-Catalyzed Domino Electrophilic Cyclization-Extended Conjugate Addition Approach
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A palladium-catalyzed domino process to access unsymmetrical diarylindolylmethanes has been developed through the annulation of o-alkynylanilines followed by 1,6-conjugate addition with p-quinone methides (p-QMs) under relatively mild conditions. The broad substrate scope of this methodology was demonstrated through the use of a wide range of substituted o-alkynylanilines and p-quinone methides, and in most cases, the unsymmetrical diarylindolylmethanes could be prepared in moderate to excellent yields. Notably, this method does not require any amino group protection. Moreover, 100% atom economy makes this transformation attractive from a green chemistry perspective.
- Reddy, Virsinha,Vijaya Anand, Ramasamy
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supporting information
p. 3390 - 3393
(2015/07/28)
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- Protonated DBU as catalyst for cascade addition-cyclization of 2-alkynylaniline and carbon disulfide
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Protonated 1,8-diazabicyclo[5,4,0]undec-7-ene as catalyst for cascade addition/cyclization of 2-alkynylaniline and carbon disulfide has been described. This process provides a convenient route for synthesis of a variety of benzo[d][1,3]thiazine-2(4H)-thio
- Zhao, Peng,Liao, Qian,Gao, Hongxin,Xi, Chanjuan
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supporting information
p. 2357 - 2361
(2013/06/26)
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- Palladium-catalyzed intermolecular aerobic oxidative cyclization of 2-ethynylanilines with isocyanides: Regioselective synthesis of 4-halo-2-aminoquinolines
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A robust and regioselective palladium-catalyzed intermolecular aerobic oxidative cyclization of 2-ethynylanilines with isocyanides to the synthesis of 4-halo-2-aminoquinolines is reported herein. The procedure constructs various 4-halo-2-aminoquinolines w
- Liu, Bifu,Gao, Hanling,Yu, Yue,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 10319 - 10328
(2013/11/06)
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- Nucleopalladation triggering the oxidative heck reaction: A general strategy to diverse β-indole ketones
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A simple and efficient palladium-catalyzed oxidative coupling between 2-alkynyl anilines and allylic alcohols is described by using cheap and green dioxygen as the oxidant. These cross-couplings have a large functional group tolerance and are of higher re
- Wang, Qian,Huang, Liangbin,Wu, Xia,Jiang, Huanfeng
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supporting information
p. 5940 - 5943
(2014/01/06)
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- Cesium carbonate-promoted hydroamidation of alkynes: Enamides, indoles and the effect of iron(III) chloride
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A series of enamide derivatives was prepared by a simple procedure for the hydroamidation of alkynes with amides and sulfonamides. The use of such a mild base as cesium carbonate promotes the latter transformation, and the addition of catalytic amounts of iron(III) chloride has a beneficial effect in the outcome of some of the presented hydroamidation reactions. A range of indoles was also synthesized from ortho-alkynylanilides by both complementary procedures, which proved to be useful for the construction of the indolo[1,2-c]quinazoline tetracyclic system from an ortho-(2-aminophenylalkynyl)anilide. Copyright
- Herrero, Maria Teresa,De Sarralde, Jokin Diaz,Sanmartin, Raul,Bravo, Laura,Dominguez, Esther
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supporting information
p. 3054 - 3064
(2013/01/15)
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- Copper-mediated cyclization-halogenation and cyclization-cyanation reactions of β-hydroxyalkynes and o -alkynylphenols and anilines
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The CuX (X = I, Br, Cl, CN)-mediated cyclization-halogenation and cyclization-cyanation reactions of β-hydroxyalkynes and o-alkynylphenol and -aniline derivatives give rise to 3-halo- and 3-cyanofuro[3,2-b]pyrroles, 3-iodo-, 3-bromo-, and 3-cyanobenzofurans, and 3-cyanoindoles, respectively.
- Swamy, Nalivela Kumara,Yazici, Arife,Pyne, Stephen G.
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supporting information; experimental part
p. 3412 - 3419
(2010/07/02)
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- Sonogashira cross-coupling reactions and construction of the indole ring system using a robust, silica-supported palladium catalyst
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The use of a recyclable silica-supported palladium catalyst in Sonogashira couplings and indole syntheses using a range of functionalised substrates is described. The catalyst is shown to be both robust and versatile, effecting the synthesis of 2-phenylindole in quantitative yield without the need for N-protection, a copper co-catalyst, a base, or a solvent. Georg Thieme Verlag Stuttgart.
- Tyrrell, Elizabeth,Whiteman, Leon,Williams, Neil
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experimental part
p. 829 - 835
(2009/07/25)
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- One-pot/four-step/palladium-catalyzed synthesis of indole derivatives: The combination of heterogeneous and homogeneous systems
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One-pot, four-step syntheses of indoles using both solid-supported heterogeneous and homogeneous palladium catalysts and reagents were carried out. Such a combination of these two-phase catalysts and reagents causes a dramatic increase in yield, and it is a simple process. The presented methodology is effective for four-step reactions to provide various functionalized indoles.
- Sakai, Hayato,Tsutsumi, Ken,Morimoto, Tsumoru,Kakiuchia, Kiyomi
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supporting information; experimental part
p. 2498 - 2502
(2009/08/14)
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- InBr3-promoted divergent approach to polysubstituted indoles and quinolines from 2-ethynylanilines: Switch from an intramolecular cyclization to an intermolecular dimerization by a type of terminal substituent group
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(Chemical Equation Presented) Use of a 2-ethynylaniline having an alkyl or aryl group on the terminal alkyne selectively produced a variety of polyfunctionalized indole derivatives in moderate to excellent yields via indium-catalyzed intramolecular cyclization of the corresponding alkynylaniline. In contrast, employment of a substrate with a trimethylsilyl group or with no substituent group on the terminal triple bond, exclusively afforded polysubstituted quinoline derivatives in good yields via indium-promoted intermolecular dimerization of the ethynylaniline. This indium catalytic system successfully accommodated the intramolecular cyclization of other arylalkyne skeletons involving a carboxylic acid and an amide group.
- Sakai, Norio,Annaka, Kimiyoshi,Fujita, Akiko,Sato, Asuka,Konakahara, Takeo
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p. 4160 - 4165
(2008/09/21)
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- Simple indole synthesis by one-pot sonogashira coupling-NaOH-mediated cyclization
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Coupling of o-iodoanilines with terminal alkynes under standard Sonogashira conditions, and further treatment with NaOH under conventional heating or microwave irradiation, afford 2-substituted indoles in usually high yields. Functionalities such as halides, nitro, and cyano groups are tolerated under the reaction conditions. Georg Thieme Verlag Stuttgart.
- Sanz, Roberto,Guilarte, Verónica,Castroviejo, M. Pilar
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scheme or table
p. 3006 - 3010
(2009/07/03)
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- Development of an Efficient Procedure for Indole Ring Synthesis from 2-Ethynylaniline Derivatives Catalyzed by Cu(II) Salts and Its Application to Natural Product Synthesis
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The development of efficient methods for the indole synthesis catalyzed by Cu(II) salts and its applications were investigated. Cu(OAc)2 has been proved to be the best catalyst for the synthesis of various 1-p-tolylsulfonyl or 1-methylsulfonylindoles, which have both electron-withdrawing and electron-donating groups on the aromatic ring and C2 position of indoles. For the primary aniline derivatives, Cu(OCOCF 3)2 showed good activities, while Cu(OAc)2 was a good catalyst for the cyclization of secondary anilines. This methodology could be applied to the sequential cyclization reaction for the compounds which have the electrophilic part in the same molecule. By prior treatment with KH, the sequential cyclization was realized to provide the tricyclic ring systems, but it was limited to five- and six-membered rings for the second cyclization. Finally, formal and total synthesis of hippadine with the Cu(II)-promoted indole synthesis as the key step was accomplished.
- Hiroya, Kou,Itoh, Shin,Sakamoto, Takao
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p. 1126 - 1136
(2007/10/03)
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- Copper-catalyzed tandem reaction between imines and alcohols leading to indoles
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A copper-catalyzed tandem reaction between 2-alkynyl-N-arylideneanilines and alcohols is found to produce N-(alkoxybenzyl)indoles in good to high yields. A wide variety of substituted N-(alkoxybenzyl)indole derivatives can be synthesized by utilizing this
- Kamijo, Shin,Sasaki, Yuya,Yamamoto, Yoshinori
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