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An efficient, mild, and metal-free approach to direct diazenylation of N-heterocyclic compounds with aryltriazenes using Br°nsted ionic liquid as a promoter has been developed for the first time. Many N-heterocyclic azo compounds were synthesized in good to excellent yields at room temperature under an open atmosphere. Notably, the promoter 1,3-bis(4-sulfobutyl)-1H-imidazol-3-ium hydrogen sulfate could be conveniently recycled and reused with the same efficacies for at least four cycles.

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Various 2-aminobenzophenones were synthesized from readily available 2-arylindoles in DMSO under O2 balloon atmosphere. The synthesis was carried out without the aid of a transition metal catalyst or moisture-sensitive organometallic reagents from 2-arylindoles.

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N-Aryl- and N-allylimines derived typically from substituted acetophenones undergo palladium(II)-catalyzed dehydrogenative cyclization reactions in the presence of tetrabutylammonium bromide and molecular oxygen in DMSO to afford indole and pyrrole derivatives, respectively, in moderate to good yields. The reactions are operationally simple and can be readily performed on multigram scales (up to 55 mmol).

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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.

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A method has been devised for the microwave-assisted, continuous-flow preparation of indole alkaloids by a two-step aryl amination/cross-coupling sequence of bromoalkenes and 2-bromoanilines. This process requires both the presence of a metal-lined flow tube (a 1180 micron capillary) and the Pd PEPPSI-IPr catalyst; without either, the catalyst or the film, there is zero turnover of this catalytic process. A silver film has been shown to provide some conversion (48-62%), but optimal results (quantitative) across a variety of bromoalkenes and bromoanilines were achieved by using a highly porous palladium film. Possible roles for the Pd film are considered, as is the interplay of the catalyst and the film.

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In the presence of palladium(II) acetate, 2-bromoanilines readily react with enamines such as N-vinylpyrrolidone or alpha-piperidinostyrene to produce indole derivatives.

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Elevated by the support: 2-Alkynyl aniline cycloisomerization to indole is catalyzed by cationic Au NPs on a carbon support. Electroneutral and rich 2-aryl indoles are further converted into 3,3?-biindoles by oxidative homocoupling that is readily catalyzed by the Au NPs on carbon, and exclusively but also somewhat sluggishly by the carbon support. Copyright

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The invention discloses a aromatic ring and [a] Carbazole compound synthesis method, which belongs to the technical field of organic synthesis. The technical scheme of the present invention to point is: connected to the 2 – phenyl indole compound, 2 – (naphthalene – 1 – yl) indole compounds or 2 – (thiazole – 1 – yl) indole compounds with the diazo compounds are dissolved in the solvent, then adding catalyst and additive, for 100 – 140 C reaction, to respectively obtain benzo [a] Carbazole compound, naphtho [a] Carbazole compound or imidazo [a] Carbazole compound. The invention relates to 2 – substituted indole compound and diazo compounds as raw materials, through the one-pot Serial reaction, aromatic ring and directly [a] Carbazole compound, synthetic process operation is convenient, mild condition, substrate and wide range of application, is suitable for industrial production. (by machine translation)

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A general and one-pot synthesis of 2-alkyl/aryl substituted indoles via a tandem Pd/C mediated coupling/5-endo-dig cyclization of terminal alkynes (including acetylenic carbinols) with o-iodoanilides in water is reported. The reaction is carried out using PPh3 and CuI as co-catalysts and 2-aminoethanol as a base. The reaction appears to tolerate a variety of functional groups present in the alkynes and does not require the use of any organic co-solvent.

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A catalytic enantioselective Mukaiyama-Mannich reaction of cyclic C-acylimines with difluoroenoxysilanes is reported. (S)-TRIP enables the enantioselective synthesis of a series of novel difluoroalkylated indolin-3-ones bearing a quaternary stereocenter in up to 97% yield and 98% ee. The synthetic utility of this protocol is highlighted by efficient conversion of the products to the corresponding indolin-3-one derivatives without any erosion of the enantiopurity.

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