Concise synthesis of pyrrolophenanthridine alkaloids using a Pd-mediated biaryl coupling reaction with regioselective C-H activation via the intramolecular coordination of the amine to Pd

The concise synthesis of Amaryllidaceae alkaloids, such as anhydrolycorinone, anhydrolycorin-7-one, assoanine, and oxoassoanine, which have a pyrrolophenanthridine skeleton, was achieved in moderate yield using the Pd-mediated biaryl coupling reaction of 1-(2-halobenzyl)-2,3-dihydroindole, which applied the regioselective C-H activation method with intramolecular coordination of the benzylamino group to Pd.     

Isolation, characterization, and theoretical study of La2@C78

A new metallofullerene, La2@C78, has been synthesized by DC arc discharge method, isolated by high-performance liquid chromatography, and characterized by laser desorption time-of-flight mass spectrometry, UV-vis-NIR absorption, differential pulse voltammetry, 13C NMR spectroscopy, and theoretical calculations. The La2@C78/CS2 solution is dark violet and presents several characteristic absorption features at 647, 561, 533, and 386 nm, with an onset around 1000 nm. With respect to empty D3-C78, the capability of La2@C78 as an electron acceptor or donor is stronger. Addition of 1,1,2,2-tetrakis(2,4,6-trimethylphenyl)-1,2-disirane to La2@C78 photochemically, as well as thermally, affords bis- and mono-adducts. Theoretical studies and 13C NMR spectroscopic analysis of La2@C78 indicate that it possesses a D3h-C78 cage (78:5).     

Ultraweak Luminescence Generated by Sweet Potato and Fusarium oxysporum Interactions Associated with a Defense Response

Abstract— Ultraweak luminescence generated by sweet potato and nonpathogenic Fusarium oxysporum interactions associated with a defense response was detected by a photoncounting method using ultrahigh-sensitive photodetectors. The time-dependent intensity variation, the spectrum and the two-dimensional imaging of the ultraweak luminescence are indicative of the defense response of the sweet potato to F. oxysporum. The production of ipomeamarone as a phytoalexin means that F. oxysporum induced the defense response in the sweet potato.     

Hole Burning and Fluorescence Spectra of Sol-Gel Derived Sm2+-Doped Glasses

Sm2+-doped glasses in the system of Al2O3-SiO2 were prepared by sol-gel processing of metal alkoxides and reacting with H2 gas at 800°C. The hole burning properties of these glasses were investigated. The holes were burned in the 7F0 5D0 line of the Sm2+ ions using a DCM dye laser at 77 K. The hole depth increased with increasing the laser irradiation time, reaching up to 15% of the total intensity within a few hundred seconds. The hole width was 3 cm–1 full width at half maximum. Fluorescence line narrowing spectra of the 5D0 7 F1 transition were analyzed to study the local structure surrounding the Sm2+ ion. It is concluded that the Sm2+ ions are closely coordinated with nine oxygens of the AlO6 group in aluminosilicate glasses and that the addition of Al3+ ions into glass induces an increase in the coordination number of the Sm2+.     

Two new acylated flavanone glycosides from the leaves and branches of Phyllanthus emblica

Two new acylated flavanone glycosides, (S)-eriodictyol 7-O-(6"-O-trans-p-coumaroyl)-beta-D-glucopyranoside (1) and (S)-eriodictyol 7-O-(6"-O-galloyl)-beta-D-glucopyranoside (2) were isolated from the leaves and branches of Phyllanthus emblica together with a new phenolic glycoside, 2-(2-methylbutyryl)phloroglucinol 1-O-(6"-O-beta-D-apiofuranosyl)-beta-D-glucopyranoside (3), as well as 22 known compounds. Their structures were determined by spectral and chemical methods.     

Optical rotary dispersion of nitrobenzene derivatives—IV : Absolute conformation of twisted nitrobenzen derivatives and its control through conformational transmission

The origin of Cotton effect shown by o-nitrobenzoyl esters is discussed. The Cotton effect observed for 1-(?)-methyl ester of 3-nitrophalic acid and 4-nitrohemimellitic acid (6 and 12), indicated that the favoured twisting direction of the nitrobenzene moiety is determined by the asymmetric menthyl group through the intervening carboxyl groups. This provides a new concept in conformational analysis of aromatic compounds. Extending the concept of conformational transmission to 2,2′-dinitrobipenhyl derivatives with known ab twisted nitrobenzene was related to the sign of the Cotton effect at 330 nm in accordance with the result of X-ray crystal analysis 1-(?)-menthyl 4-bromo-2-nitrobenzoate (1)     

Experimental determination of ionization potentials of tetraphenylporphine and metallotetraphenylporphines

Gas-phase ionization potentials of tetraphenylporphine and some metallotetraphenylporphines have been determined by the method of photocurrent measurements in nonpolar solvents reported previously [1]. The values obtained range from 5.9 to 6.3 eV, depending on the central metal ion, correlating well with the reported polarographic oxidation potentials. It has been concluded that photoelectron ejection from these complexes in isooctane occurs from the porphyrin π-system in all cases including Co(II) tetraphenylporphine, in which the electron is thought to be removed from the metal in polar solvents.     

Charge-induced spin alignment in diradical donor molecules: numerical calculations of correlated many-electron-spin systems

The mechanism of charge-induced high spin is studied in pi-conjugated molecules by means of a model-Hamiltonian approach. Intersite Coulomb interactions are taken into account in a pi-conjugated moiety, which is coupled with two localized spins through exchange interactions. We clarify spin alignment in neutral and oxidized states by exact numerical calculations including all the correlation effects. In thianthrene-based molecules, one-electron oxidation induces strong ferromagnetic correlation between the localized spins irrespective of the spin alignment in the neutral state. The localized spins are coupled to the delocalized hole spin ferromagnetically, leading to a high-spin state in the oxidized molecule. Our calculations on structural dependence and effective exchange interaction are consistent with the recent experiment of thianthrene bis(nitronyl nitroxide). By comparing the thianthrene-based molecule with the anthracene-based one, we clarify the role of superexchange interactions via the sulfur atoms.     

Alkane Oxidation with Molecular Oxygen Using a New Efficient Catalytic System: N-Hydroxyphthalimide (NHPI) Combined with Co(acac)(n)() (n = 2 or 3)

A novel class of catalysts for alkane oxidation with molecular oxygen was examined. N-Hydroxyphthalimide (NHPI) combined with Co(acac)(n)() (n = 2 or 3) was found to be an efficient catalytic system for the aerobic oxidation of cycloalkanes and alkylbenzenes under mild conditions. Cycloalkanes were successfully oxidized with molecular oxygen in the presence of a catalytic amount of NHPI and Co(acac)(2) in acetic acid at 100 degrees C to give the corresponding cycloalkanones and dicarboxylic acids. Alkylbenzenes were also oxidized with dioxygen using this catalytic system. For example, toluene was converted into benzoic acid in excellent yield under these conditions. Ethyl- and butylbenzenes were selectively oxidized at their alpha-positions to form the corresponding ketones, acetophenone, and 1-phenyl-1-butanone, respectively, in good yields. A key intermediate in this oxidation is believed to be the phthalimide N-oxyl radical generated from NHPI and molecular oxygen using a Co(II) species. The isotope effect (k(H)/k(D)) in the oxidation of ethylbenzene and ethylbenzene-d(10) with dioxygen using NHPI/Co(acac)(2) was 3.8.