C‐2 Selective Arylation of Indoles with Heterogeneous Nanopalladium and Diaryliodonium Salts

A simple and efficient method to prepare synthetically useful 2‐arylindoles is presented, using a heterogeneous Pd catalyst and diaryliodonium salts in water under mild conditions. A remarkably low leaching of metal catalyst was observed under the applied conditions. The developed protocol is highly C‐2 selective and tolerates structural variations both in the indole and in the diaryliodonium salt. Arylations of both N?H indoles and N‐protected indoles with ortho‐substituted, electron‐rich, electron‐deficient, or halogenated diaryliodonium salts were achieved to give the desired products in high to excellent isolated yields within 6 to 15 h at room temperature or 40 °C.     

Influence of glottal closure configuration on vocal efficacy in young normal-speaking women

Posterior closure insufficiency of the glottis is often mentioned in connection with permanent voice disorders. Recently published studies have revealed that an incomplete closure of the glottis can be found also in normal-speaking voices, especially in women. However, the effect of glottal closure configuration on vocal efficacy is not sufficiently clarified. The purpose of this study was to determine the effect of glottal closure configuration on singing and speaking voice characteristics. Overall, 520 young female normal-speaking subjects were examined by videostroboscopy for different phonation conditions in the combination of soft, loud, low, and/or high phonation and by voice range profile measurements. According to the videostroboscopic analysis, the subjects were subdivided into four groups: complete closure of the vocal folds already in soft phonation (group 1), closure of the vocal fold with increasing intensity (group 2), persistent closure insufficiencies despite increasing intensity (group 3), and hourglass-shaped closure in subjects with vocal nodules (group 4). Subjects in which the glottal closure could not be evaluated sufficiently were subclassified into group 5 (missing values).

Selected criteria of the singing and speaking voice were evaluated and statistically processed according to the mentioned subclassification. Group 1 reached significantly the highest sound pressure levels (SPL_max) for the singing voice as well as for the shouting voice. Group 3 showed a limited capacity to increase the intensity of the singing and speaking voice. The results gathered in this study objectify the relationship of insufficient glottal closure and reduced vocal capabilities. As long as no conclusive data on long-term consequences of insufficient glottal closure are available, a prophylactic improvement of the laryngeal situation especially in female professional voice users by voice therapy should be recommended.     

Electron-poor N-substituted imide-fused corannulenes

N-Substituted imide-fused corannulenes can be generated from the corresponding tetramethylfluoranthenes. Syntheses, crystal structure and electronic properties are reported. The solid state structure of the pentafluorophenyl derivative shows nearly perfect π-stacking in a convex-concave fashion and is expected to possess useful electronic properties.     

Stereospecific Photoredox-Catalyzed Vinylations to Functionalized Alkenes and C-Glycosides**

We report an efficient radical-mediated C−C coupling through photoredox-catalyzed reactions of 4-alkyl-dihydropyridines (DHPs) and vinylbenziodoxol(on)es (VBX, VBO). This transition-metal-free and mild photocatalytic method has excellent functional group tolerance and affords vinylated products in good yields, with complete retention of the alkene configuration. The utility of the methodology is demonstrated by the diastereoselective synthesis of C-vinyl glycosides. Preliminary mechanistic studies suggest that the C−C bond formation is stereospecific and proceeds through a concerted radical coupling transition state.     

A regio- and stereodivergent route to all isomers of vic-amino alcohols

Vicinal amino alcohols are substructures in several important natural products. They are also frequently employed ligands in asymmetric synthesis. Many enantioselective syntheses of vic-amino alcohols have been reported, but each structure has required its own synthetic route. This study presents a synthetic strategy leading to all eight possible isomers of a given beta-amino alcohol, starting from vinyl epoxides. The developed strategy focuses on the propensity of vinyl epoxides and vinylaziridines to be selectively ring-opened at the allylic position by suitable hard nucleophiles. Within this strategy, a novel large-scale aminolysis reaction and the synthesis of a trisubstituted N-H vinylaziridine are detailed.