Borocyclic Radicals Prepared from Orthoquinone-Containing Polycyclic Aromatics by Photoirradiation.

Borocyclic radicals with highly conjugated aromatics were generated from orthoquinone-containing polycyclic aromatic compounds by trapping the photoinduced triplet state with simple boron halide under irradiation with light of appropriate wavelength. The picene-based borocyclic radical was remarkably stable when stored at 23 °C in a desiccator for over 1 year. The crystal structure of this stable radical had a stacking structure of a planar π-conjugated system, and the electrical conductivity was higher than those of ordinary organic radical systems.

Quadruply N-methylated octaphyrin: a helical macrocycle exhibiting chiroptical properties and dynamic conformation changes correlated with helical and inner N-methyl orientations.

[38]Octaphyrin(1.1.1.1.1.1.1.1) bearing four methyl moieties at the inner nitrogen sites has been synthesized. This expanded porphyrin has helical chirality as correlated with the orientations of the inner N-methyl groups, exhibiting chiroptical properties as observed in CD Cotton effects from the enantiomers through optical resolution. The chirality of the octaphyrin was retained at r.t. but the racemization occurred at higher temperature as examined by CD spectral changes. The dynamic conversion processes between the enantiomers were investigated by theoretical studies, suggesting the plausible pathways via the intermediates with appropriate conformations.

Redox Switching of Orthoquinone-Containing Aromatic Compounds with Hydrogen and Oxygen Gas.

Unique redox switching of orthoquinone-containing pentacyclic aromatic compounds with molecular hydrogen and oxygen in the presence of a palladium nanoparticle catalyst (SAPd) is disclosed. These molecules were predicted by in silico screening before synthesis. Efficient protocols for the synthesis of orthoquinone-containing aromatic compounds by palladium-mediated homocoupling and the benzoin condensation reaction were developed. Clear switching between orthoquinone and aromatic hydroquinone compounds was observed on the basis of their photoluminescence properties. Furthermore, the twist strain of the orthoquinone moiety could induce dramatic changes in color and emission.

Diaryliodonium Salt-Mediated Intramolecular C-N Bond Formation Using Boron-Masking N-Hydroxyamides.

Intramolecular aromatic C-N bond formation reactions using electron-rich aromatic tethered boron-masking N-hydroxyamide as substrate were realized. These new C-N bond formation reactions involve the in situ generation of a diaryliodonium salt by treatment with hypervalent iodine, deborylation by base treatment, spontaneous N → O acyl migration, cyclization, reductive elimination, elimination of benzoic acid, and tautomerization to indole formation. Hereby, we obtained highly functionalized electron-rich indoles and quinoline in practical yields.

α-Ketocarbenium Ions Derived from Orthoquinone-Containing Polycyclic Aromatic Compounds.

α-Ketocarbenium ions derived from synthesized orthoquinone-containing polycyclic aromatic compounds were generated in the presence of Brønsted acids such as sulfuric acid, trifluoromethanesulfonic acid, and fluorosulfonic acid. The prepared α-ketocarbenium ions were stabilized by conjugation of the aromatic moiety. In addition, unique absorption properties of the α-ketocarbenium ions were observed and identified on the basis of the calculated absorption spectra. It was suggested that the zigzag-shaped architecture stabilizes the newly discovered α-ketocarbenium ions derived from orthoquinone-containing polycyclic aromatic compounds.