Pd-catalyzed 5-endo-trig-type cyclization of β,γ-unsaturated carbonyl compounds: an efficient ring closing reaction to give γ-butenolides and 3-pyrrolin-2-ones

The 5-endo-trig-type cyclization has been performed using a Pd-bis(isoxazoline) catalyst. The present cyclization of β,γ-unsaturated carbonyl compounds gave γ-butenolides and 3-pyrrolin-2-ones in good to excellent yields.     

Asymmetric Catalysis with Heterobimetallic Compounds

This review focuses on a new concept in catalytic asymmetric reactions that was first realized for the use of heterobimetallic complexes. As these heterobimetallic complexes function as both a Brønsted base and as a Lewis acid, just like an enzyme, they make possible a variety of efficient catalytic asymmetric reactions. This heterobimetallic concept should prove to be applicable to a variety of new asymmetric catalyses. The first part of this review describes the development of rare-earth–alkali metal complexes such as LnM₃tris(binaphthoxide) complexes (LnMB, Ln = rare-earth metal, M = alkali metal), which are readily prepared from the corresponding rare-earth trichlorides or rare-earth isopropoxides, and their application to catalytic asymmetric synthesis. By using a catalytic amount of LnMB complexes several asymmetric reactions proceed efficiently to give the corresponding desired products in up to 98% ee: LnLB-catalyzed asymmetric nitroaldol reactions (L = Li), LnSB-catalyzed asymmetric Michael reactions (S ? Na), and LnPB-catalyzed asymmetric hydrophosphonylations of either imines or aldehydes (P ? K). Applications of these heterobimetallic catalysts to the syntheses of several biologically and medicinally important compounds are also described. Spectral analyses and computational simulations of the asymmetric reactions catalyzed by the heterobimetallic complexes reveal that the two different metals play different roles to enhance the reactivity of both reaction partners and to position them. From mechanistic considerations, a useful activation of the heterobimetallic catalyses was realized by addition of alkali metal reagents. The second part describes the development of another type of heterobimetallic catalysts featuring Group 13 elements such as Al and Ga as the central metal. Among them, the AlLibis(binaphthoxide) complex (ALB) is an effective catalyst for asymmetric Michael reactions, tandem Michael–aldol reactions, and hydrophosphonylation of aldehydes.     

Fusion of photochromic reaction and synthetic reaction: photoassisted cyclization to highly strained chiral azobenzenophanes

A method for synthesizing highly strained cyclic structures by combining photochromic and synthetic reactions is described. Tightly linked azobenzene-binaphthyl dyads (R)-4 and (R)-6 could not be obtained by conventional cyclization, but continuous application of photoirradiation, which induced (E)→(Z) isomerization of the azobenzene moiety, allowed the cyclization reaction to proceed, affording the desired chiral azobenzenophanes.     

Bottom-up synthesis of optically active oligonaphthalenes: three different pathways for controlling axial chirality

The oxidative homocoupling of optically active binaphthalenes 1a-d with a stoichiometric amount of CuCl2 and amines afforded quaternaphthalenes 2a-d in up to 93% de. The high diastereoselectivities were achieved through three different pathways (epimerization of the axis together with diastereoselective crystallization, thermodynamic, and kinetic control pathways). The type of side chains on the naphthalene influenced which pathway dominates. Three pathways were applicable to octinaphthalenes (8a-d) and hexadecanaphthalene 10a with 46-99% de. The absolute configuration of the newly formed axial bond was determined by (1) X-ray crystallographic analysis, (2) transformation to known compounds 15 and 16, (3) CD spectra of oligonaphthalenes with two pyrene rings as exciton parts, and (4) the shift values in 13C NMR spectra of 13C-enriched derivatives 29-31 toward chiral shift reagent Eu(+tfc)3.     

Single-shot femtosecond electron diffraction with laser-accelerated electrons: experimental demonstration of electron pulse compression

We report the first experimental demonstration of longitudinal compression of laser-accelerated electron pulses. Accelerated by a femtosecond laser pulse with an intensity of 101? W/cm2, an electron pulse with an energy of around 350 keV and a relative momentum spread of about 10?2 was compressed to a 500-fs pulse at a distance of about 50 cm from the electron source by using a magnetic pulse compressor. This pulse was used to generate a clear diffraction pattern of a gold crystal in a single shot. This method solves the space-charge problem in ultrafast electron diffraction.     

Kinetic analysis of the mechanolysis of polymethylmethacrylate in the course of vibratory ball milling at various mechanical energy

We carried out the mechanolysis of polymethylmethacrylate (PMMA) at various mechanical energies and analyzed kinetically the mechanoradical concentration and molecular weight at various mechanical energies. The radical concentration gradually increased to a maximum and then gradually decreased after reaching the maximum value. It is suggested that the radical quenching reaction (disproportionation and/or recombination) progressed together with radical formation. Kinetic analysis of the mechanoradical concentration indicated that the actual amounts of mechanoradicals produced were larger than observed. It is also suggested that vast numbers of reactions take place in mechanolysis. The molecular weight decreased exponentially toward the limiting value, and the limiting molecular weight was larger with decreases in mechanical energy. It is also suggested that mechanoradical formation is inversely proportional to the change in molecular weight at any given mechanical energy. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4161–4167, 2004     

Deficits in spatial learning and motor coordination in ADAM11-deficient mice

Background  

ADAM11 is a member of the ADAM gene family and is mainly expressed in the nervous system. It is thought to be an adhesion molecule, since it has a disintegrin-like domain related to cell-cell or cell-matrix interactions. To elucidate the physiological functions of ADAM11, we generated ADAM11-deficient mice by means of gene targeting.     

Enantioselective oxidative-coupling of polycyclic phenols

Enantioselective oxidative-coupling of polycyclic phenols, such as 2-anthracenol, 9- or 3-phenanthrol, and 5-chrysenol was established by using vanadium(V/IV) catalysis under air or O₂ as a co-oxidant. In the vanadium catalyzed reaction, the corresponding coupling products were obtained in good to excellent yields with up to 93% enantiomeric excess.     

Thermally Stable Super Ionic Conductor from Carbon Sphere Oxide

A highly stable proton conductor has been developed from carbon sphere oxide (CSO). Carbon sphere (CS) generated from sucrose was oxidized successfully to CSO using Hummers’ graphite oxidation technique. At room temperature and 90 % relative humidity, the proton conductivity of thin layer CSO on microsized comb electrode was found to be 8.7×10^?3 S cm^?1, which is higher than that for a similar graphene oxide (GO) sample (3.4×10^?3 S cm^?1). The activation energy (E_a) of 0.258 eV suggests that the proton is conducted through the Grotthuss mechanism. The carboxyl functional groups on the CSO surface are primarily responsible for transporting protons. In contrast to conventional carbon‐based proton conductors, in which the functional groups decompose around 80 °C, CSO has a stable morphology and functional groups with reproducible proton conductivity up to 400 °C. Even once annealed at different temperatures at high relative humidity, the proton conductivity of CSO remains almost unchanged, whereas significant change is seen with a similar GO sample. After annealing at 100 and 200 °C, the respective proton conductivity of CSO was almost the same, and was about ～50 % of the proton conductivity at room temperature. Carbon‐based solid electrolyte with such high thermal stability and reproducible proton conductivity is desired for practical applications. We expect that a CSO‐based proton conductor would be applicable for fuel cells and sensing devices operating under high temperatures.