Ten new Lycopodium alkaloids having the lycopodane skeleton isolated from Lycopodium serratum Thunb

Ten new alkaloids, lycoposerramines-F (1), -G (2), -H (3), -I (4), -J (5), -K (6), -L (7), -M (8), -N (9), and -O (10), having lycopodine-related structures, were isolated from the club moss Lycopodium serratum THUNB. and their structures were elucidated on the basis of spectroscopic analysis and/or chemical transformation.     

Kinetic resolution of racemic α-tert-alkyl-α-hydroxy esters by enantiomer-selective carbamoylation

Kinetic resolution of sterically hindered racemic α-tert-alkyl-α-hydroxy esters is performed by enantiomer-selective carbamoylation with the t-Bu-Box-Cu(II) catalyst (Box = bis(oxazoline)). The reaction with 0.5 equiv of n-C(3)H(7)NCO is carried out with a substrate-to-catalyst molar ratio of 500-5000 at -20 to 25 °C. The high enantiomer-discrimination ability of the catalyst achieves an excellent stereoselectivity factor (s = k(fast)/k(slow)) of 261 in the best case. A catalytic cycle for this reaction is proposed.     

Electrocatalytic Oxidation of Amines on a Mediator‐Modified Electrode by Electrochemical Copolymerization of Nitroxyl Radical Precursor Containing Pyrrole Side Chain and Bithiophene

This paper describes the electrocatalytic oxidation of amines on TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl)‐modified electrodes prepared by electrochemical copolymerization of TEMPO precursor containing pyrrole side chain and 2,2′‐bithiophene. The modified electrode exhibits electrocatalytic activity for the oxidation of primary and secondary amines. Cyclic voltammetric studies showed that the peak current of the cyclic voltammogram increased linearly with increasing concentration of amine in the sample solution.     

A Cu(II)-mediated C-H oxygenation of sterically hindered tripyridine ligands to form triangular Cu(II)3 complexes

Two sterically hindered tris-pyridyl methane ligands, tris(6-methyl-2-pyridyl)methane (L1) and bis(6-methyl-2-pyridyl)pyridylmethane (L2), are newly synthesized. Under aerobic conditions, Ln (n = 1 or 2) reacts with CuX2 (X = Cl or Br), oxygenated at the methine position to LnOH or LnOMe. The former alcoholate ligand creates trinuclear Cu(II) complexes [Cu3(X)(LnO)3](PF6)2 [(X, n) = (Br, 1) 1, (C1, 1) 2, (Br, 2) 3, or (C1, 2) 4] in which the alkoxide oxygen atoms bridge copper centers. The crystal structures of 1-4 are presented along with their magnetic susceptibility data. The weak antiferromagnetic coupling between the Cu(II) centers in this trinuclear arrangement is due to weak interaction of the magnetic orbitals (dz2) which are oriented along three alternate sides in a hexagon of the Cu3O3 core in 1-4. Under anaerobic conditions, L1 reacts with CuBr2 to form a square pyramidal complex [CuL1Br2] (9) with the ligand facially capping. [Cu(Br)2(L1OMe)] (10) was obtained after the suspension of 9 in MeOH was stirred under air for 48 h. In the presence of cyclohexene, 9 is converted to [Cu(Br)(L1)]m (m = 1 or 2) 5 quantitatively to give trans- 1,2-dibromocyclohexane, indicating that Br2 is generated during the reaction. The FAB MS spectrum of [18O]-1 prepared by the reaction of L1 with CuBr2 under 18O2 shows that the ligand of [18O]-1 is L1(18O-.) L1(18OH), L1OCD3, and bis(6-methyl-2-pyridyl) ketone were obtained from reaction of L1 with CuBr2 in CD3OD under 18O2. These results indicate that the origins of the O atom in L1OH and L1OMe are O2 and MeOH, respectively. On the basis of these results, a mechanism of the oxygenation of L1 in the present system will be proposed.     

Schulzeines A-C, new alpha-glucosidase inhibitors from the marine sponge Penares schulzei

Three new alpha-glucosidase inhibitors, schulzeines A-C (1-3), were isolated from the marine sponge Penares schulzei. Their structures were elucidated by spectral analysis and chemical degradations to be the isoquinoline alkaloids, encompassing two amino acids, and C(28) fatty acid, the last of which was sulfated. Absolute stereochemistry of schulzeines was determined by application of the modified Mosher analysis to fragments obtained by chemical degradation. Schulzeines A-C inhibit alpha-glucosidase with IC(50) values of 48-170 nM.     

Synthesis of a highly luminescent three-dimensional pyrene dye based on the spirobifluorene skeleton

We have synthesized a highly luminescent (log e > 5.0, F > 0.9) pyrene dye based on a spirobifluorene skeleton [2,2',7,7'-tetrakis(7-tert-butyl-1-pyrenyl)-9,9'-spirobi[9H-fluorene; 4-PySBF]. The use of spirobifluorene prevents fluorescence quenching by intramolecular energy transfer and/or electron transfer among the chromophores in the excited state. The emission spectra of 4-PySBF exhibited a red shift of 20 nm in comparison to a model compound [9,9'-dioctyl-2,7-bis(7-tert-butyl-1-pyrenyl)-9H-fluorene; 2-PyF], but its UV-Vis spectrum remained unchanged.     

Specifications of a neutron exposure accelerator system for biological effects experiments (NASBEE) in NIRS

We developed a neutron irradiation facility, neutron exposure accelerator system for biological effect experiments (NASBEE) for biological studies in National Institute of Radiological Sciences, Japan. Irradiation field of 2 MeV average neutrons generated by a Be(d–n)B reaction is established. Dose uniformity of 240 mm in diameter irradiation field is producible within ±2.5% with a dose rate of 0.87 Gy/h at sample target distance of 1170 mm. Two irradiation rooms, a specific pathogen-free (SPF) conditioned one and a conventional, are now available. Irradiation protocols for in vitro experiments are now established and demonstrated by obtaining a relative biological effectiveness (RBE) of cell inactivation measured to be 3.54 with 10% survival dose (D₁₀).     

Fiber-packed needle-type sample preparation device designed for gas chromatographic analysis

A miniaturized sample preparation technique that uses a fine-fiber-packed needle as the extraction medium is reviewed, especially in relation to its application to the analysis of volatile organic compounds by gas chromatography. When the needle was packed longitudinally with a bundle of fine filaments (12 μm o.d.) which were also surface-coated with polymeric materials, successful sample preconcentration was obtained. Improved sensitivity was also established by introducing simultaneous derivatization reactions into the extraction process in the fiber-packed needle. The storage performance of the needle clearly demonstrated the potential of the technique for typical on-site sampling during environmental analysis. In this short review, the fiber-packed extraction needle developed by the authors is summarized along with applications that use the fiber-packed needle as a miniaturized extraction device.     

[2,3]‐Wittig Rearrangement of Enantiomerically Enriched 3‐Substituted 1‐Propenyloxy‐1‐phenyl‐2‐propen‐1‐yl Carbanions: Effect of Heteroatoms and Conjugating Groups on Planarization of an α‐Oxy‐Benzylcarbanion through a Double Bond

Don't get trapped : The effect of conjugating electron‐withdrawing groups and α‐anion‐stabilizing heteroatom substituents on configurational stability of chiral carbanions through a double bond was examined on the basis of extent of chirality transfer in intramolecular trapping in [2,3]‐Wittig rearrangement of chiral 3‐substituted 1‐propenyloxy‐1‐phenyl‐2‐propen‐1‐yl carbanions (see scheme).