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A Reusable MOF-Supported Single-Site Zinc(II) Catalyst for Efficient Intramolecular Hydroamination of o-Alkynylanilines

The exploitation of new and active earth-abundant metal catalysts is critical for sustainable chemical production. Herein, we demonstrate the design of highly efficient, robust, and reusable ZnII-bipyridine-based metal?organic framework (MOF) catalysts for the intramolecular hydroamination of o-alkynylanilines to indoles. Under similar conditions homogeneous catalytic systems mainly provide hydrolysate. Our results prove that MOFs support unique internal environments that can affect the direction of chemical reactions. The ZnII-catalyzed hydroamination reaction can be conducted without additional ligands, base, or acid, and is thus a very clean reaction system with regard to its environmental impact.

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Cascade alkenyl amination/heck reaction promoted by a bifunctional palladium catalyst: A novel one-pot synthesis of indoles from o-haloanilines and alkenyl halides

A novel approach for the synthesis of the important indole ring is described. Indoles are obtained from o-bromoanilines and alkenyl halides in a Pd-catalyzed cascade process that involves an alkenyl amination followed by an intramolecular Heck reaction. The overall process represents the first example of the participation of alkenyl amination reactions in Pd-catalyzed cascade reactions. Initially, the relative reactivity of aryl and alkenyl bromides and chlorides towards Pd-catalyzed amination was investigated. Competition experiments were carried out in the presence of primary and secondary amines, and these revealed the reactivity order alkenyl bromides > aryl bromides > alkenyl chlorides > aryl chlorides, as well as very high chemoselectivity; the more reactive halide was always favored. Thereafter, optimized reaction conditions for the sequential alkenyl amination/Heck cyclization to give indoles were investigated with the model reaction of o-bromoaniline with a-bromostyrene. An extensive screening of ligands, bases, and reaction conditions revealed that the [Pd2(dba)3]/ DavePhos, NaOtBu, toluene combination at 100C were the optimized reaction conditions to carry out the cascade process (dba = dibenzylideneacetone, DavePhos = 2-dicyclohexylphosphino-2′-N,N-dimethylaminobiphenyl). The reaction proceeds with aryl, alkyl, and functionalized substitutents in both starting reactants. The cyclization was also studied with N-substituted o-bromoanilines (which would give rise to N-substituted indoles); however, in this case, indole formation occurred only with 1-substituted-2-bromoalkenes. Finally, the application of this methodology to 0-chloroanilines required further optimization. Although the catalyst based on DavePhos failed to promote the cascade process, a catalytic combination based on [Pd2(dba)3]/X-Phos promoted the formation of the indole ring also from the less reactive chloroanilines.

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Enantioselective arylative dearomatization of indoles via pd-catalyzed intramolecular reductive heck reactions

A highly enantioselective intramolecular arylative dearomatization of indoles via palladium-catalyzed reductive Heck reactions was developed. The new strategy led to a series of optically active indolines bearing C2-quaternary stereocenters in modest to good yields with excellent enantioselectivities (up to 99% ee).

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Synthesis of 2-substituted indoles via Pd/C-catalyzed reaction in water

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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Rhodium-catalyzed NH-indole-directed ortho C?H coupling of 2-arylindoles with diazo compounds via metal carbene migratory insertion

A high regioselective rhodium-catalyzed ortho C?H coupling of 2-arylindoles with diazo compounds via NH-indole-directed C?H bond activation has been developed. The catalytic reaction features mild reaction conditions, broad substrate scope and good functional group tolerability.

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Copper-Catalyzed Synthesis of 2-Arylquinazolinones from 2-Arylindoles with Amines or Ammoniums

A novel copper-catalyzed synthesis of quinazolinones from easily available 2-arylindoles and amines or ammoniums has been developed, which provided various quinazolinones in up to 99% yields for 43 examples. This strategy features tolerance of a wide range of functional groups, easily available starting materials, simple operation, mild reaction conditions, and environmental friendliness.

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Chiral Br¡ãnsted Acid from Chiral Phosphoric Acid Boron Complex and Water: Asymmetric Reduction of Indoles

A new chiral Br¡ãnsted 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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An intramolecular cascade cyclization of 2-aryl indoles: Efficient methods for the construction of 2,3-functionalized indolines and 3-indolinones

Efficient intramolecular N/O-nucleophilic cyclization of 2-aryl indoles has been developed to afford the corresponding 2-aza-3-oxaindolines and 3-indolinones in 80-95% yield. The methods provided convenient access to fused imidazo[1,2-c]oxazolidinone, oxazolidine, or tetrahydro-1,3-oxazine cores under mild conditions. This journal is the Partner Organisations 2014.

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Relay Catalysis of Bismuth Trichloride and Byproduct Hydrogen Bromide Enables the Synthesis of Carbazole and Benzo[alpha]carbazoles from Indoles and alpha-Bromoacetaldehyde Acetals

Benzo[alpha]carbazoles were synthesized from 2-phenylindoles and alpha-bromoacetaldehyde using bismuth trichloride as a catalyst. The reaction was triggered by a bismuth trichloride-catalyzed Friedel-Crafts alkylation of these two precursors, which provided a tryptaldehyde intermediate that underwent intramolecular olefination to form the final product. Interestingly, the HBr byproduct generated in the upstream step of the reaction catalyzed the following downstream reaction steps, thus creating a byproduct-participated relay catalytic process. Motivated by this mechanism, we developed a three-component reaction of indole, alpha-bromoacetaldehyde acetal, and 1,3-dicarbonyl compounds. This study offers a straightforward method for synthesizing substituted carbazoles. (Figure presented.).

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Heterobimetallic cobalt/rhodium nanoparticle-catalyzed carbonylative cycloaddition of 2-alkynylanilines to oxindoles

(Chemical Equation Presented) The cobalt-rhodium heterobimetallic nanoparticle-catalyzed synthesis of oxindoles from 2-alkynylanilines in the presence of carbon monoxide is described.

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