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Versatile borylations of C(sp2)?H and C(sp3)?H were achieved with ruthenium(II) biscarboxylate complexes. The robust nature of the ruthenium(II) catalyst enabled C(sp3)?H borylation on pyrrolidines, piperidines, and azepanes with ample scope and excellent positional selectivity control.

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Two protocols for ruthenium- or palladium-catalyzed direct arylations In user-friendly polyethylene glycol (PEG) were devised, which set the stage for the development of user-friendly paliadium(0)-cataiyzed C-H bond functionalizations In the presence of air with a recyclable phosphlne ligand-free palladium complex.

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An efficient CoIII-catalyzed three-component strategy to prepare homoallylic alcohols containing acyclic quaternary centers is disclosed. This transformation enables the introduction of two C?C sigma bonds through C?H bond activation and sequential addition to internally substituted dienes and a wide range of aldehydes and activated ketones. Isoprene and other internally monosubstituted dienes are effective inputs, with the reaction proceeding with high diastereoselectivity for those substrate combinations that result in more than one stereogenic center. Moreover, the opposite relative stereochemistry can be achieved by employing 1,2-disubstituted dienes. A mechanism for the transformation is proposed based upon the relative stereochemistry of the products and studies with isotopically labeled starting materials.

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We report here a manganese-catalyzed C-H methylation reaction of considerable substrate scope, using MeMgBr, a catalytic amount of MnCl2· 2LiCl, and an organic dihalide oxidant. The reaction features ambient temperature, low catalyst loading, typically 1%, high catalytic turnover reaching 5.9 × 103, and no need for an extraneous ligand and illustrates a unique catalytic use of simple manganese salts for C-H activation, which so far has relied on catalysis by manganese carbonyls.

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Getting a handle on it: In the chelation-assisted title reactions in the presence of a hypervalent iodine oxidant, sodium azide and sodium nitrite served as readily available nitrogen sources, and pyridine, pyrimidine, and pyrazole substituents were efficient directing groups (DGs; see scheme; Cp=C 5Me5). The synthetic utility of the azidation products was demonstrated in subsequent functional-group transformations. Copyright

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Facile synthesis of 5-fluoropyrazoles by direct fluorination of pyrazoles with N-fluorobenzenesulfonimide (NFSI) was elaborated. This approach was used to prepare the unsubstituted 5-fluoro-1H-pyrazole, the known fungicide Penflufen, and many functionalized 5-fluoropyrazoles: building blocks for medicinal chemistry and agrochemistry.

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An efficient, unprecedented reactivity of Cp?Co(III) for the synthesis of tetrasubstituted allenes under mild conditions is disclosed. Electron-rich and highly nucleophilic cobalt facilitates the dehydrative C-H bond allenylation directly from propargylic alcohols without any derivatization. The reaction proceeds via reversible cyclometalation followed by alcohol-directed regioselective alkyne insertion and beta-hydroxy elimination to provide the tetrasubstituted allenes.

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A Ru-catalyzed oxidative coupling of arenes with boronic acids using molecular oxygen via direct C-H activation is reported. Both the scope and the mechanism of the process are discussed.

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Mechanistic studies revealed ruthenium-catalyzed direct arylations to proceed through reversible C-H bond activation and subsequent rate-limiting oxidative addition with aryl halides, which led to the development of widely applicable well-defined ruthenium(II) carboxylate catalysts.

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This paper details the copper-catalyzed N-arylation of pi-excessive nitrogen heterocycles. The coupling of either aryl iodides or aryl bromides with common nitrogen heterocycles (pyrroles, pyrazoles, indazoles, imidazoles, and triazoles) was successfully performed in good yield with catalysts derived from diamine ligands and CuI. General conditions were found that tolerate functional groups such as aldehydes, ketones, alcohols, primary amines, and nitriles on the aryl halide or heterocycle. Hindered aryl halides or heterocycles were also found to be suitable substrates using the conditions reported herein.

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