Generation of 6-(Trifluoromethyl)-4,5-dihydro-2(3H)-pyridone and the Application to Synthesis of Some Fused Nitrogen Heterocycles Carrying a Trifluoromethyl Group on the Bridgehead Position via Radical Cyclization of Dihydropyridones

Staudinger/aza-Wittig reaction of 6,6,6-trifluoro-5-oxohexanoyl azide with PPh(3) or PBu(3) was examined. A reactive intermediate acyl imine 1 was trapped by methanol. Without nucleophile, isomerized enamide form 3 was obtained. N-Iodobenzoylation and N-haloalkylation of 3 and following radical cyclization via the 5-exo or 6-exo mode gave benzoindolizidinone, indolizidinone, and quinolizidinone derivatives 10-14, which have a trifluoromethyl group at the bridgehead position adjacent to nitrogen. Although LiAlH(4) reduction of 10 and 11 gave a mixture of saturated benzoindolizidine 15 and amino alcohol 16, reduction with BH(3)/THF selectively gave the desired 15 and indolizidine 17 from 13.     

Isolation and Stereostructures of Dolastatin G and Nordolastatin G, Cytotoxic 35-Membered Cyclodepsipeptides from the Japanese Sea Hare Dolabella auricularia

A bioassay-directed fractionation of the cytotoxic constituents of the Japanese sea hare Dolabella auricularia resulted in the isolation of two 35-membered depsipeptides dolastatin G (1) and nordolastatin G (2), which showed cytotoxicity against HeLa S(3) cells with IC(50) values of 1.0 and 5.3 &mgr;g/mL, respectively. The gross structures of these substances were established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure of 1 was determined by chiral HPLC analysis of amino acid components obtained from acid hydrolysis of 1 and by the enantioselective syntheses of two degradation products arising from polyketide portions. Nordolastatin G (2) is a congener that has the same absolute stereochemistry as that of 1.     

Quasi-classical limit of Toda hierarchy andW-infinity symmetries

Previous results on quasi-classical limit of the KP hierarchy and itsW-infinity symmetries are extended to the Toda hierarchy. The Planck constant now emerges as the spacing unit of difference operators in the Lax formalism. Basic notions, such as dressing operators, Baker-Akhiezer functions, and tau function, are redefined.W _{1 +} symmetries of the Toda hierarchy are realized by suitable rescaling of the Date-Jimbo-Kashiara-Miwa vertex operators. These symmetries are contracted tow _{1 +} symmetries of the dispersionless hierarchy through their action on the tau function.     

Information theory of miniaturization advantages of column liquid chromatography for quantitative analysis

Summary The influences of decreasing column diameter and length on two analytical goals, the precision and solvent efficiency, in reversed-phase liquid-chromatography are studied. Low solvent consumption is one of analytical advantages of miniaturized columns and is shown to be quantitatively evaluated by the precision and solvent efficiency which are defined to be the total Shannon mutual information obtained from an assay and the information obtained in a unit solvent volume, respectively. Analysis of paraben food additives on a microbore column is taken as an example. In trace analysis, the relative standard deviation (RSD) of measurements theoretically derived from the precision is shown to approach to the observed ones.     

Benzoyl(acetylacetonato)nickel(II) complexes containing tertiary phosphine ligands. Their synthesis,dynamic behavior in solution,and decarbonylation

Carbon monoxide is readily inserted into the phenyl—nickel bond of PhNi(acac)(PR₃)_n to give benzoylnickel complexes, PhCONi(acac)PR₃ (R = Ph, Et, cyclo-C₆H₁₁), which were characterized by elemental analysis, IR and NMR spectroscopy, as well as chemical reactions. The reactions of the benzoylnickel complexes with methyl iodide and alcohols give acetophenone and corresponding benzoates, respectively, accompanied by some decomposition reactions. The solid benzoylnickel complexes when heated at elevated temperatures are decarbonylated and biphenyl, benzophenone and carbon monoxide are liberated. The dynamic behavior of the acac ligand in acetone solution was studied and the activation parameters for the acac exchange reactions were obtained. The decarbonylation reaction of the benzoyl complex PhCONi(acac)PPh₃ in acetone was studied by NMR, and found to be first order in the benzoylnickel complex.     

Parallel synthesis of multi-branched oligosaccharides related to elicitor active pentasaccharide in rice cell based on orthogonal deprotection and glycosylation strategy

We describe a parallel and efficient synthesis of multi-branched oligosaccharides 3a-g based upon the structure of the phytoalexin elicitor active branched pentasaccharide 2. One-pot sequential orthogonal deprotection of tetrasaccharide 5 with three different protecting groups provided each of seven glycosyl acceptors 4a-g. Glycosylation of the acceptors 4a-g, followed by deprotection provided branched oligosaccharides 3a-g. All the reaction processes from scaffold 5 to 3a-g except for final hydrogenolysis were achieved utilizing an automated synthesizer in a parallel fashion.     

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.     

Halide-free dehydrative allylation using allylic alcohols promoted by a palladium-triphenyl phosphite catalyst

The triphenyl phosphite-palladium complex was found to effect catalytic substitution reactions of allylic alcohols via a direct C-O bond cleavage. The dehydrative etherification proceeded efficiently without any cocatalysts and bases to give allylic ethers in good to excellent yields.     

Vibronic interactions in negatively charged polyacetylene

Electron-phonon interactions in the monoanions of polyacetylenes such as C2H4 (2tpa), C4H6 (4tpa), C6H8 (6tpa), and C8H10 (8tpa) are studied and compared with those in the monoanions of polyacenes. The C-C stretching A(g) modes around 1500 cm(-1) the most strongly couple to the lowest unoccupied molecular orbitals (LUMO) in polyacetylenes. The estimated total electron-phonon coupling constants for the monoanions (l(LUMO)) are 0.579, 0.555, 0.463, and 0.401 eV for 2tpa, 4tpa, 6tpa, and 8tpa, respectively. The l(LUMO) values for polyacetylenes are much larger than those for polyacenes. Furthermore, the l(LUMO) value for polyacetylene with C(2h) geometry is estimated to be 0.254 eV, and is larger than that (0.024 eV) for polyacene with D(2h) geometry. The phase patterns difference between the LUMO of polyacenes localized on the edge part of carbon atoms, and the delocalized LUMO of polyacetylenes is the main reason for the calculated results. The single charge transfer through the molecule in polyacetylenes are also discussed. The reorganization energies between the neutral molecule and the corresponding monoanion are estimated to be 0.164, 0.144, 0.125, and 0.113 eV for 2tpa, 4tpa, 6tpa, and 8tpa, respectively. Such reorganization energy decreases with an increase in molecular size. The conditions under which the attractive electron-electron interactions are realized in the monoanions of polyacetylenes and polyacenes are discussed. In terms of the electron-phonon interactions and the reorganization energies, the relationships between the normal and possible superconducting states are briefly discussed. We find that the monoanions with smaller molecular size cannot easily become good conductors, however, the conditions under which the interactions between two electrons are attractive are more easily realized in the monoanions with smaller molecular size than in the monoanions with larger molecular size.