The Ir(III)-catalyzed direct α-C−H amidation of imidazole-masked aliphatic carboxylic acids with dioxazolones is reported. The presence of an imidazole moiety as a directing group is a key to the success of the reaction. The products can be easily converted to esters and amides in a simple procedure. The reaction shows a broad substrate scope for various substituted 2acylimidazoles, as well as a variety of dioxazolone derivatives with important functional groups being tolerated. The reaction mechanism was investigated by deuterium-labeling experiments, Hammett plots, NMR, and FAB-MS, and we propose the generation of an iridium nitrene intermediate.
The selective, Rh(I)-catalyzed ortho-C-H alkylation of biologically important aryl sulfonamides with maleimides with the aid of an 8-aminoquinoline directing group is reported. The reaction exhibits a good substrate scope.
The rhodium(I)-catalysed reaction of aromatic amides that contain a 2-(methylthio)aniline directing group with maleimides gives isoindolone spirosuccinimides as products under aerobic, metal oxidant-free, and solvent-free conditions. In sharp contrast to...
General. Chemicals and solvents were purchased from commercial suppliers or purified by standard techniques. For thin-layer chromatography (TLC), silica gel plates (Merck 60 F 254 ) were used and compounds were visualized by irradiation with UV light and/or by treatment with a solution of phosphomolybdic acid in ethanol followed by heating. Flash column chromatography was performed using KANTO silica gel 60N (particle size 63-210 µ m). 1 H NMR and 13 C NMR spectra were recorded on JEOL JNM-AL spectrometer at ambient temperature. Chemical shifts are given in δ relative to tetramethylsilane (TMS), the coupling constants J are given in Hz. The spectra were recorded in CDCl 3 as solvent at ambient temperature, TMS served as internal standard (δ = 0 ppm) for 1 H NMR and CDCl 3 was used as internal standard (δ = 77.0) for
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