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A Pd(II)-catalyzed oxidative coupling between pyridine N-oxides and N-substituted indoles via 2-fold C-H bond activation was achieved with high selectivity using Ag2CO3 as an oxidant.

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Diketene is an ideal molecule for use in many organic transformations, since it possesses electrophilic and nucleophilic sites which react with numerous functional groups. Diketene is mostly used as the common starting material for structurally diverse mono-, spiro-, and fused six-membered heterocycles such as lactones, pyrans, pyridines, quinolines, isoquinolines, oxazine, quinoxalines, benzothiazinone, 1,4-thiazidines, and oxazinonethione.

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A simple, one-pot procedure is described for the direct conversion of quinoline N-oxides to alpha-amidoquinolines with primary amides. This methodology is complimentary to the Abramovich reaction, which is limited to the introduction of secondary amides via imidoyl chlorides. Although reaction conditions are quite similar, omission of the base is key for successful reaction with primary amides, which were found not to proceed through the intermediacy of an imidoyl chloride but rather through an acyl isocyanate.

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The scope and mechanistic implications of the direct transformation of heterocyclic N-oxides to 2-trifluoromethyl-, and related perfluoroalkyl- and perfluoroaryl-substituted N-heterocycles has been studied. The reaction is effected by perfluoroalkyl- and perfluorophenyltrimethylsilane in the presence of strong base. In situ displacement of the para-fluoro substituent in the pentafluorophenyl ring and the methoxy group in 8-methoxyquinolines with additional nucleophiles allows for further site-selective refunctionalization of the N-heterocyclic products. This journal is the Partner Organisations 2014.

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We have demonstrated that the unsupported nanoporous gold (AuNPore) was a green and highly efficient heterogeneous catalyst for the reduction of amides to amines using hydrosilanes as reductants. A variety of tertiary amides with a broad functional groups were reduced to the corresponding tertiary amines in the presence of 2 mol% of AuNPore and PheMe2SiH or (Me2SiH)2O under mild conditions. AuNPore catalyst was recovered by simple filtration and used for twelve times without any loss of catalytic activity. The AuNPore/hydrosilane system was also successfully applied to the hydrosilative reduction of sulfoxides and N-oxides. (Figure presented.).

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A general and facile one-pot procedure for the synthesis of 2-substituted pyridines from the corresponding pyridine-N-oxides and nucleophiles is presented as a mild alternative to SNAr chemistry. A variety of nucleophiles and heterocyclic-N-oxides participate effectively in this transformation, which uses the phosphonium salt, PyBroP, as a means of substrate activation.

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(Chemical Equation Presented) An alternative to pyridine: Pyridine-N-oxides undergo direct C-H activation and add across alkynes under mild nickel catalysis to afford (E)-2-alkenylpyridine-N-oxides in modest to good yields with high selectivity. Subsequent deoxygenation and deoxygenative functionalization proceed smoothly to give a wide variety of 2-substituted pyridines. PCyp 3 = tricyclopentylphosphine, cod = cyclooctadiene.

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A cascade reaction of isoquinoline N-oxides with alkynones was developed, delivering a fluorescent benzoazepino[2,1-a]isoquinoline derivative. The reaction worked smoothly without requirement of any catalyst or additive, making this method economical and easy to handle.

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Organocatalytic functionalization of heteroaromatic N-oxides was investigated using in situ generated onium amide bases, and C-nucleophiles were efficiently introduced by the sequential addition-elimination reaction under metal-free conditions, affording 2-substituted nitrogen heteroaromatics generally in good to high yields. The Royal Society of Chemistry 2013.

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A general method of preparation of derivatives of bis(o-azaheteroaryl)methanes from aromatic N-oxides is reported, the key step of which is a 1,3-dipolar cycloaddition between N-oxides of azines or azoles and in situ generated terminal difluoroalkenes containing an o-azaheteroaryl substituent at the double bond. Selected products were applied for the preparation of two novel unsymmetrical analogues of BODIPY fluorescent dyes, containing both an imidazole and a quinoline or isoquinoline unit.

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