Regioselective allylmetalation of allenes with tetraallylmanganate or allylmagnesium chloride under MnCl2 catalysis

[reaction: see text] Treatment of allenes with tetraallylmanganate provides allylated products with high regioselectivity. A catalytic amount of MnCl(2) combined with allylmagnesium chloride also achieves efficient allylmetalation of allenes. The resulting alkenylmagnesium species react with various electrophiles. In the presence of molecular oxygen, the alkenylmagnesium undergoes diallylation reaction. A cyclization reaction of 1,2,6-heptatriene with tetraallylmanganate is also described.     

Selective halogen-magnesium exchange reaction via organomagnesium ate complex

Halogen-magnesium exchange of various aryl halides is achieved with a magnesium ate complex at low temperatures. Tributylmagnesate (nBu3MgLi) induces facile iodine-magnesium exchange at -78 degrees C. Dibutylisopropylmagnesate (iPr(n)Bu2MgLi) is more reactive than nBu3MgLi, and this reagent accomplishes selective bromine-magnesium exchange at -78 degrees C. This procedure is utilized for the preparation of various polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using this method proceeds with retention of configuration of the double bond.     

Multiple Coulomb excitation of a 70Ge beam and the interpretation of the 02 + state as a deformed intruder

Electromagnetic properties of the low-lying states in a ⁷⁰Ge nucleus were studied through the multiple Coulomb excitation of a ⁷⁰Ge beam with a ^natPb target. Relative γ-ray intensities were measured as a function of emission angle relative to the scattered projectile. Sixteen E2 matrix elements, including diagonal ones, for 6 low-lying states have been determined using the least-squares search code GOSIA. The expectation values 〈Q ²〉 of 0₁ ⁺ and 0₂ ⁺ states in ⁷⁰Ge are compared with those in ^{72, 74, 76}Ge. Simple mixing calculations indicate that the 0₂ ⁺ states in ⁷⁰Ge and ⁷²Se can be treated as deformed intruder states. It is shown that the deformed intruder becomes the ground state in ⁷⁴Kr. These interpretations of the 0₂ ⁺ states in this region are compared with the potential-energy surface calculations by the Nilsson-Strutinsky model, which allow to interpret the experimental results in a qualitative way from the theoretical point of view. Received: 2 September 2002 / Accepted: 5 November 2002 / Published online: 25 February 2003 RID="a" ID="a"e-mail: sugawara@pf.it-chiba.ac.jp Communicated by D. Schwalm     

Total Valuation Rings of Ore Extensions

We consider extensions of a total valuation ring V of a skew field K to the Ore extension K(X;σ, δ) for an endomorphism σ of K and a σ-derivation δ. It is shown that there exists an extension R of V with X ∈ R, such that ${\overline X}$ is transcendental over V/J(V) if and only if (σ,δ) is compatible with V, where ${\overline X} = X + J(R^(1))$ . In the case V is invariant, it is established that there is an invariant extension R of V in K(X;σ,δ) such that ${\overline X}$ is transcendental if and only if σ(a)V = aV and δ(a) ∈ aV for all a ∈ K.     

Formation of organomagnesium compounds via EtMgBr-mediated radical cyclization of allyl beta-iodoacetals

[reaction: see text] Treatment of allyl beta-iodoacetals with ethylmagnesium bromide in THF provided tetrahydrofuran derivatives in good yields. On the other hand, the reaction in DME provided tetrahydrofuranylmethylmagnesium compounds in good yields.     

Initial-state parton shower kinematics for NLO event generators

We are developing a consistent method to combine tree-level event generators for hadron collision interactions with those including one additional QCD radiation from the initial-state partons, based on the limited leading-log (LLL) subtraction method, aiming at an application to NLO event generators. In this method, a boundary between non-radiative and radiative processes necessarily appears at the factorization scale (μ_F). The radiation effects are simulated using a parton shower (PS) in non-radiative processes. It is therefore crucial in our method to apply a PS which well reproduces the radiation activities evaluated from the matrix-element (ME) calculations for radiative processes. The PS activity depends on the applied kinematics model. In this paper we introduce two models for our simple initial-state leading-log PS: a model similar to the ’old’ PYTHIA-PS and a p_T-prefixed model motivated by ME calculations. PS simulations employing these models are tested using W-boson production at LHC as an example. Both simulations show a smooth matching to the LLL subtracted W+1 jet simulation in the p_T distribution of W bosons, and the summed p_T spectra are stable against a variation of μ_F, despite that the p_T-prefixed PS results in an apparently harder p_T spectrum.     

Synthesis, structure, and properties of extended π-conjugated systems bearing sterically crowded triarylphosphines

The sterically crowded triarylphosphines bearing formyl and benzoyl groups were synthesized and characterized by X-ray crystallography. The benzoyl derivative was converted to the p-quinomethane conjugated with the triarylphosphine. The McMurry coupling of the formyl derivative afforded the diarylethene bearing the two sterically-crowded-triarylphosphine moieties. The cyclic voltammograms of these compounds show reversible redox waves corresponding to the oxidation to the radical cations of the triarylphosphines and irreversible or quasi-reversible waves corresponding to the reduction of the acceptor moieties. The electronic and the fluorescence spectra of these π-conjugated systems, especially push-pull substituted derivatives, exhibit bathochromic shift typical of the extended π-conjugated systems especially in the polar solvent, and the large Stokes shift typical of the crowded triarylphosphines is enhanced by conjugation with the acceptor moiety.     

Solubilization of C60 by micellization with a thermoresponsive block copolymer in water: Characterization,singlet oxygen generation,and DNA photocleavage

Water‐soluble diblock copolymer, poly(N‐isopropylacrylamide)‐block‐poly(N‐vinyl‐2‐pyrroridone) (PNIPAM_m‐b‐PNVP_n), was found to associate with fullerene (C₆₀), and thus C₆₀ can be solubilized in water. The 63C₆₀/PNIPAM_m‐b‐PNVP_n micelle formed a core‐shell micelle‐like aggregate comprising a C₆₀/PNVP hydrophobic core and a thermoresponsive PNIPAM shell. The C₆₀‐containing polymer micelle formation and its thermoresponsive behavior were characterized using light scattering and ¹H NMR techniques. The hydrodynamic radius (R_h) of the C₆₀‐bound polymer micelle increased with increasing temperature, which was ascribed to the hydrophobic association between dehydrated PNIPAM shells above lower critical solution temperature (LCST). ¹H NMR data suggest that the motion of the PNIPAM block is restricted above LCST due to the dehydration of the PNIPAM shell in water. The generation of singlet oxygen by photosensitization by the C₆₀‐bound polymer micelle was confirmed from photooxidation of 9,10‐anthracenedipropionic acid. Furthermore, DNA was found to be cleaved by visible light irradiation in the presence of the C₆₀‐bound polymer micelle. Therefore, there may be a hope for a pharmaceutical application of the C₆₀‐bound polymer micelle to cancer photodynamic therapy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.