Novel approach with amide-tethered H-bond donor NHC ligands enabled Au(I)-catalysis via H-bonding. The plain NHC-Au(I)-Cl complex catalysed conversions of terminal N-propynamides to oxazolines, and enyne cycloisomerization with an acid additive,...
A simple “reagent-free” thermal air treatment turns active carbon into a mildly oxidized material with an increased quinoidic content that catalytically dehydrogenates saturated N-heterocycles to the corresponding aromatic compounds. Additional...
HNO 3 -oxidized carbon nanotubes catalyze oxidative dehydrogenative (ODH) carbon-carbon bond formation between electron-rich (hetero)aryls with O 2 as a terminal oxidant. The recyclable carbocatalytic method provides ac onvenient and an operationally easy synthetic protocol for accessing various benzofused homodimers, biaryls, triphenylenes, and related benzofused heteroaryls that are highly useful frameworks for material chemistry applications.C arbonyls/quinones are the catalytically active site of the carbocatalyst as indicated by model compounds and titration experiments.F urther investigations of the reaction mechanism with ac ombination of experimental and DFT methods support the competing nature of acid-catalyzed and radical cationic ODHs, and indicate that both mechanisms operate with the current material.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.
A photoreductive
protocol utilizing [Ru(bpy)3]2+ photocatalyst,
blue light LEDs, and ascorbic acid (AscH2) has been developed
to reduce nitro N-heteroaryls to the corresponding
anilines. Based on experimental and computational results and previous
studies, we propose that the reaction proceeds via proton-coupled
electron transfer between AscH2, photocatalyst, and the
nitro N-heteroaryl. The method offers a green catalytic procedure
to reduce, e.g., 4-/8-nitroquinolines to the corresponding aminoquinolines,
substructures present in important antimalarial drugs.
Cuneane is a strained hydrocarbon that can be accessed via metal-catalyzed isomerization of cubane. The carbon atoms of cuneane define a polyhedron of the C 2v point group with six faces�two triangular, two quadrilateral, and two pentagonal. The rigidity, strain, and unique exit vectors of the cuneane skeleton make it a potential scaffold of interest for the synthesis of functional small molecules and materials. However, the limited previous synthetic efforts toward cuneanes have focused on monosubstituted or redundantly substituted systems such as permethylated, perfluorinated, and bis(hydroxymethylated) cuneanes. Such compounds, particularly rotationally symmetric redundantly substituted cuneanes, have limited potential as building blocks for the synthesis of complex molecules. Reliable, predictable, and selective syntheses of polysubstituted cuneanes bearing more complex substitution patterns would facilitate the study of this ring system in myriad applications. Herein, we report the regioselective, Ag I -catalyzed isomerization of asymmetrically 1,4-disubstituted cubanes to cuneanes. In-depth DFT calculations provide a charge-controlled regioselectivity model, and direct dynamics simulations indicate that the nonclassical carbocation invoked is short-lived and dynamic effects augment the charge model.
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