Studies on the syntheses of analgesics. Part 50. Synthesis of optically active 2-[4-(1-oxo-2-isoindolinyl)phenyl]propanoic acid. [Studies on the syntheses of heterocyclic compounds. Part 742]

2-[4-(1-Oxo-2-isoindolinyl)phenyl]propanoic acid ( 1 ) having a potent analgesic and anti-inflammatory activity could be obtained by three methods, which were found to provide extremely useful ways for the synthesis of 1 from the industrial point of view. (E)- and (Z)-Isomers of 2-butenoic acid and oxiranecarboxylic acid derivatives as the intermedaites in the synthesis of 1 were separated and characterized. Furthermore, the optical resolution of (±)-2-[4-(1-oxo-2-isoindolinyl)phenyl]propanoic acid was successfully achieved using cinchonidine as a resolution reagent.     

Synthesis of chiral [5]helicenes using aromatic oxy-Cope rearrangement as a key step

Both enantiomers of (P)-(+)-2- and (M)-(−)-2-acetoxy-11,14-dimethyl[5]helicenes 8 were synthesized by asymmetric aromatic oxy-Cope rearrangement of the corresponding chiral bridged bicyclic compounds, which were obtained by enzymatic resolution. The absolute configurations of 8 were assigned by their circular dichroism spectra.     

Charge separation in a nonfluorescent donor-acceptor dyad derived from boron dipyrromethene dye, leading to photocurrent generation

Boron dipyrromethene (BODIPY), which is commonly used as an energy absorbing and transferring antenna molecule, has been modified to contain an electron donor moiety, 8-(2,4,5-trimethoxyphenyl)-4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (MEOPHBDP). The photoinduced electron transfer from a 2,4,5-trimethoxyphenyl moiety to a BODIPY moiety of MEOPHBDP in acetonitrile was observed by femtosecond laser flash photolysis measurements. The lifetime of the charge-separated state of MEOPHBDP was 59 ps at 298 K. The dye-sensitized solar cells (DSSC) were prepared using MEOPHBDP with carboxylic acid (MEOPHBDP-COOH) and a reference BODIPY dye having no electron donor moiety. The photovoltaic measurements were performed using a standard two-electrode system consisting of a working electrode and a Pt sputtered electrode in methoxyacetonitrile containing 0.5 M iodide and 0.05 M I(2). The photoelectrochemical properties of DSSC with MEOPHBDP are compared with those with a reference BODIPY dye.     

Superconductivity in heavy fermion systems

The heavy fermion state in the f-electron systems is due to competition between the RKKY interaction and the Kondo effect. The typical compound is CeCu₆. To understand the electronic state, we studied the Fermi surface properties via the de Haas–van Alphen (dHvA) experiment and energy band calculation for CeSn₃,CeRu₂Si₂,UPt₃, and nowadays, transuranium compounds. Pressure is also an important technique to control the electronic state. The Néel temperature T_N decreases with increasing pressure P and becomes zero at the critical pressure for . The typical compound is an antiferromagnet CeRhIn₅, which we studied from the dHvA experiment under pressure. A change of the 4f-electronic state from localized to itinerant is realized at , revealing the first-order phase transition, together with a divergent tendency of the cyclotron mass at P_c. It is stressed that appearance of superconductivity in CeRhIn₅ is closely related to the heavy fermion state. It is also noted that the parity-mixed novel superconducting state might be realized in a pressure-induced superconductor CeIrSi₃ without inversion symmetry in the crystal structure.     

Local magnetic field and muon site in CeAs

We report on zero field and longitudinal field μSR experiments on a CeAs single crystal between 3.3 and 12 K. Below the antiferromagnetic transition at 7.5 K a spontaneously precessing signal with a saturation frequency of \approx25 MHz representing the full sample amplitude has been found. From an analysis of the field dependence of the relaxation rate of this signal in \langle 100\rangle and \langle 110\rangle crystal orientation parallel to the muon spin and the applied longitudinal field, a \langle 100\rangle orientation of the local field at the muon site is concluded. This supports an AF‐I single‐\veck magnetic ordering. This revised version was published online in July 2006 with corrections to the Cover Date.     

KINETICS AND MECHANISM OF PHOTOCYCLOADDITION OF DEOXYURIDINES TO 2,3-DIMETHYL-2-BUTENE

The mechanism of photocycloaddition of 2′-deoxyuridine (1a) and thymidine (1b) to 2,3-dimethyl-2-butene (Bu) in acetonitrile by UV irradiation has been studied. The reciprocal quantum yield for the cycloaddition increased linearly with reciprocal concentrations of Bu in acetonitrile to give limiting quantum yields at infinite concentration of Bu as 0.030 and 0.0096 for 1a and 1b , respectively. This shows that the cycloaddition proceeds in a two-step mechanism between the triplet state of 1 and Bu through biradical intermediates. Addition of cis-1,3-pentadiene quenched the reaction obeying the Stern–Volmer equation. The above quenching experiments and laser transient spectroscopy revealed that the triplet state of 1a reacts with Bu with much larger rate constant (1.3–1.6 × 10⁹ M^?1 s^?1) than that of 1b (4–5 × 10⁷ M^?1 s^?1) reflecting larger steric hindrance exerted in the reaction of 1b than that of 1a .