An improved synthesis of （-）-7-isopropyl-cis-1-amino-2-indanol the chiral auxiliary for 6π-azaelectrocyclization

(-)-7-Isopropyl-cis-1-amino-2-indanol, a key chiral auxiliary and ligand in the highly stereo-selective asymmetric 6π-azaelectrocyclization, has been prepared previously by two methods. Each however involved using of one extreme condition, i.e. high temperature or high pressure, for the respective reaction. A modified reaction route employed mild condition for synthesis was presented in this report.     

Palladium-catalyzed asymmetric 6-endo cyclization of dienamides with substituent-driven activation

Chiral 2-piperidinone compounds with various C-6 substituents were successfully synthesized via a Pd-catalyzed asymmetric 6-endo cyclization of dienamides, which were evidently activated by both N-p-toluenesulfonyl and C-3 ester substituents.     

Pulse radiolysis studies of intermolecular charge transfers involving tryptophan and three-electron-bonded intermediates derived from methionine

The oxidation processes of the radiation-generated, three-electron-bonded intermediates AcMet₂ [S??S]⁺ and AcMet [S??Br] were investigated by pulse radiolysis via their reactions with tryptophan (TrpH). These intermediates were derived from N-acetyl-methionine amide (N-AcMetNH₂) and N-acetyl-methionine methyl ester (N-AcMetOMe). The bimolecular rate constant k of the reaction between each intermediate and l-tryptophan (TrpH) was measured. For N-AcMetNH₂, k for the reaction of AcMet₂ [S??S]⁺ with TrpH were 3.4?×?10⁸ and 2.2?×?10⁸?dm³?mol^?1?s^?1 at pH?=?1 and 4.5, respectively. For N-AcMetOMe, k for the reaction of AcMet₂ [S??S]⁺ with TrpH were 4.0?×?10⁸ and 2.8?×?10⁸?dm³?mol^?1?s^?1 at pH 1 and 4.5, respectively. The rate constants for the intermolecular transformation of Met [S??Br] into TrpH⁺ or Trp were also estimated. For N-AcMetNH₂, k for the reaction of AcMet₂ [S??Br] with TrpH were 2.6?×?10⁸ and 3.3?×?10⁸?dm³?mol^?1?s^?1 at pH 1 and 4.5, respectively. Related mechanisms were discussed.     

Lewis Acid-Catalyzed Intramolecular [2 + 2] Cycloaddition of alpha-Ester-Substituted Conjugated Dienyl- and Trienylphosphonates. New Synthesis of Functionalized Cyclic Terpenoids

alpha-Ester-substituted 1,3-dienylphosphonates 7 and 8, prepared by the Knoevenagel condensation, underwent intramolecular [2 + 2] cycloaddition in the presence of Lewis acid to form bicyclo[4.2.0] (26-57% yield) and bicyclo[3.2.0]skeleton (14-38% yield), respectively. Similar treatment of homologous 1,3-dienylphosphonate 11 and 1,3,5-trienylphosphonate 12 resulted in the formation of ionone derivatives (30-94% yield). The intramolecular cycloaddition reaction was applicable to several conjugated dienes bearing an ester group.     

A new continuation method for complementarity problems with uniformP-functions

The complementarity problem with a nonlinear continuous mappingf from the nonnegative orthantR ₊ ⁿ ofR ⁿ intoR ⁿ can be written as the system of equationsF(x, y) = 0 and(x, y) R ₊ ²ⁿ , whereF denotes the mapping from the nonnegative orthantR ₊ ²ⁿ ofR ²ⁿ intoR ₊ ⁿ × Rⁿ defined byF(x, y) = (x ₁y₁,,x_ny_n, f₁(x) – y₁,, f_n(x) – y_n) for every(x, y) R ₊ ²ⁿ . Under the assumption thatf is a uniformP-function, this paper establishes that the mappingF is a homeomorphism ofR ₊ ²ⁿ ontoR ₊ ⁿ × Rⁿ. This result provides a theoretical basis for a new continuation method of tracing the solution curve of the one parameter family of systems of equationsF(x, y) = tF(x ⁰, y⁰) and(x, y) R ₊ ²ⁿ from an arbitrary initial point(x ⁰, y⁰) R ₊ ²ⁿ witht = 1 until the parametert attains 0. This approach is an extension of the one used in the polynomially bounded algorithm recently given by Kojima, Mizuno and Yoshise for solving linear complementarity problems with positive semi-definite matrices.     

Fullerene as a standard sample for adjusting the NMR spectral resolution in multiple-quantum magic-angle-spinning experiments.

A method using fullerene for adjusting the NMR spectral resolution for multiple quantum magic angle spinning (MQMAS) experiments is proposed. To observe its (13)C MAS signal, it is not necessary to apply (1)H decoupling, unavailable with single-resonance MQMAS probes. Although (13)C T(1) of fullerene is rather long, a recycle time of 5 s in shimming yields its signal with sufficiently high sensitivity if setting the appropriate Ernst angles corresponding to magnetic fields. It is demonstrated that so-adjusted high resolution is reflected in the (87)Rb MQMAS spectra of RbNO(3).     

Synthesis of sphingomyelin difluoromethylene analogue

As a new sphingomyelinase inhibitor, a novel sphingomyelin CF₂ analogue was designed and synthesized. One key step of this synthesis is the very mild hydrolysis of the oxazolidinone ring, a suitable intermediate for the introduction of a diethyl difluoromethylphosphonate group, by utilizing the characteristic electron withdrawing nature of the nosyl group at the oxazolidinone ring in an alcoholic solvent to produce the corresponding carbonate attaching at the secondary hydroxy group. The synthesized CF₂ analogue inactivated toward B. cereus sphingomyelinase with nearly the same attitude as the nitrogen analogue that we previously reported.     

Quantitative analysis of the temperature effect on the radiation crosslinking and scission of polyethylene macromolecules

The γ-radiation-induced crosslinking of low-density polyethylene over a wide temperature range was studied with a new log–logarithmic scale method for sol–gel analysis. A straight line was always obtained for the plotting of log (sol fraction) against log (dose). Gel points were accurately obtained from the plot intersects, and scission/crosslinking ratios were obtained from the plot slopes via computer simulations with GelSim6 software. The crosslinking and scission yields were determined to be 0.17 and 0.078 mmol/kJ, respectively, at 30 °C, and they increased to 2.3 and 4.4 mmol/kJ, respectively, at 300 °C. The observed regularities are explained by the fact that enhanced macromolecular motion decreases the cage effect on recombination reactions in the polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1656–1661, 2001     

Aggregation of photolytic gold nanoparticles at the surface of chitosan films

Formation and aggregation of photolytic gold nanoparticles at the surface of chitosan (CTO) films have been investigated. When thin films of chloroauric acid salt of CTO were irradiated with UV light in wet air at room temperature for 10 min, gold nanoparticles of approximately 10 nm size are formed at the film surface. Detailed X-ray photoelectron spectroscopy (XPS) study and field emission type scanning electron microscopy (FE-SEM) observation have been carried out to characterize gold nanoparticles at the film surface. The shift of Au(4f) peak to the higher energy side and broadening of full width at half-maximum in the XPS spectrum are the direct evidence of the existence of gold atoms and small clusters in the early stage of photolysis. According to FE-SEM observation, growth in the particle diameter and aggregation of nanoparticles were observed after prolonged irradiation, and, finally, the film surface was densely covered with gold particles of 20-100-nm size. Gold atoms and clusters could move in the film and precipitate to the irradiated surface. Chemical composition analysis further suggests that gold particles at the surface are covered with an ultrathin CTO layer, which is partly oxidized by oxygen and chlorinated by chlorine during photochemical reactions.     

Temperature dependence of radiation effects in polyethylene: Cross‐linking and gas evolution

High‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) were irradiated in vacuo at 30–220 and 30–360°C, respectively, with γ‐rays at doses of 10–400 kGy. Temperature dependence of cross‐linking and gas evolution was investigated. It was found that cross‐linking was the predominant process up to 300°C and the gel point decreased smoothly with temperature. The increase of G(x) with temperature was likely attributed to the temperature effect on addition of radicals to the double bonds present in the polymer. Above 300°C, the gel fraction at a given dose decreased remarkably with temperature and turned to zero at 360°C. The molecular weight variation determined with gel permeation chromatography (GPC) indicated the enhanced degradation at 360°C by radiation. G‐values of H₂ increased with temperature and varied with dose. The compositions of the C₁–C₄ hydrocarbons evolved depended on the structures of side branches. Raising the temperature favored the formation of unsaturated hydrocarbons, and the yield of unsaturated relative to saturated hydrocarbons decreased with dose. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1541–1548, 1999