Regioselective hydroformylation of allylic alcohols

A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of β-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen.     

Development and implementation of Høgdahl convention and Westcott formalism for k<Subscript>0</Subscript>-INAA application at Malaysian Nuclear Agency reactor

The present work shows the development of k₀-instrumental neutron activation analysis (k₀-INAA) method at the Malaysian Nuclear Agency research reactor. To use the k₀-INAA method, two formalisms were regulated according to 1/ν and non-1/ν (n, γ) reaction nuclides. The reactor neutron spectrum parameters, the thermal to epithermal neutron flux ratio (f), the epithermal neutron flux shape factor (α) were measured using the bare bi-isotopic monitor and bare triple monitor methods, respectively, based on the Høgdahl convention. In addition, the modified spectral index \( r(\alpha )\sqrt {T_{n} /T_{0} } \), the Westcott \( g_{Lu} (T_{n} ) \) factor and the absolute neutron temperature T _n parameters were determined using the Westcott formalism. ¹⁷⁶Lu was used as non- 1/ν monitor while ¹⁹⁷Au, ⁹⁶Zr and ⁹⁴Zr were used as 1/ν monitors. The average values of \( r(\alpha )\sqrt {T_{n} /T_{0} } ,\,g_{Lu} (T_{n} ) \) and T _n were determined to be 0.1795 ± 0.0044, 1.9729 ± 0.0234 and 50.12 ± 3.21°C, respectively. The accuracy of the method was evaluated by analysing IAEA-Soil 7, IAEA-SL 1, NBS SRM 1633A-1 and IAEA-Soil 375 as reference materials. The results show an acceptable level of consistency.     

Time- and wavelength-interleaved optical pulse train generation based on dispersion spreading and sectional compression

A method to generate time- and wavelength-interleaved optical pulse trains based on dispersion spreading and sectional compression is proposed and demonstrated. A 4×2 GHz time- and wavelength-interleaved pulse train is generated from an input 2 GHz mode-locked pulse train. The advantages of the proposed scheme are its simplicity and robustness, since no microwave component or multiwavelength laser source is required. In addition, we demonstrate supercontinuum generation of an ultraflat 18 nm bandwidth spectrum with less than 0.5 dB fluctuation over the 3.2 nm central bandwidth.     

Noise conversion from pump to the passively mode-locked fiber lasers at 1.5 μm

We characterize the noise conversion from the pump relative intensity noise (RIN) to the RIN and phase noise of passively mode-locked lasers at 1.5 μm. Two mode locking mechanisms, nonlinear polarization rotation (NPR) and semiconductor saturable absorber mirror (SESAM), are compared for noise conversion for the first time. It is found that the RIN and the phase noise of both types of lasers are dominated by the noise converted from the pump RIN and thus, can be predicted with the measured pump RIN and noise conversion ratios. The SESAM laser is found to show an excess noise conversion from the laser RIN to the laser phase noise due to the slow saturable absorber effect.     

Tin-free radical alkoxyamine addition and isomerization reactions by using the persistent radical effect: variation of the alkoxyamine structure

Various C-centered radicals can efficiently be generated through thermal C-O-bond homolysis of alkoxyamines. This method is used to perform environmentally benign radical cyclization and intermolecular addition reactions. These alkoxyamine isomerizations and intermolecular carboaminoxylations are mediated by the persistent radical effect (PRE). In the paper, the effect of the variation of the alkoxyamine structure--in particular steric effects in the nitroxide moiety--on the outcome of the PRE mediated radical reactions will be discussed. Fourteen different nitroxides were used in the studies. It will be shown that reaction times can be shortened about 100 times upon careful tuning of the alkoxyamine structure. Activation energies for the C-O-bond homolysis of the various alkoxyamines are provided. The kinetic data are used to explain the reaction outcome of the PRE-mediated processes.     

upper bond 1 start]PdCl[PPh(2)CH(2)CH(2)C[upper bond 1 end]HCH(2)CH(2)PPh(2)] as a precursor to homo- and hetero-metallic species directed by ESMS (electrospray ionisation mass spectrometry)

The cyclometallated Pd compound [upper bond 1 start]PdCl[PPh(2)CH(2)CH(2)C[upper bond 1 end]HCH(2)CH(2)PPh(2)], obtained from PdCl(2)(Ph(2)P(CH(2))(5)PPh(2)) in refluxing DMF (N,N-dimethylformamide), was characterized by NMR and X-ray single-crystal diffraction analysis. The cyclometallation of MCl(2)(Ph(2)P(CH(2))(5)PPh(2))(M = Pd, Pt) to give and its Pt(ii) analogue was probed using electrospray ionisation mass spectrometry (ESMS). The reactivity of towards neutral ligands such as phosphines and pyridines as well as basic metal complexes such as pyridine-thiolate compounds of Au(i), Hg(ii) and Pt(ii) in solution was also investigated. The results showed that the chloride trans to the Pd-C bond is susceptible to ligand replacement. A number of entry metalloligands was examined in an attempt to establish a route to cyclometallated aggregates and clusters.     

The reaction of N-isocyaniminotriphenylphosphorane (NICITPP) with some of cyclic ketones and a primary amine in the presence of 3-phenyl-2-propynoic acid

The 1:1 imine intermediate generated by the addition of a primary amine to a cyclic ketone is trapped by N-isocyaniminotriphenylphosphorane in the presence of 3-phenyl-2-propynoic acid and the corresponding iminophosphorane intermediate was formed. Disubstituted 1,3,4-oxadiazole derivatives are formed via intramolecular aza-Wittig reaction of the iminophosphorane intermediate. The reactions were completed in neutral conditions at room temperature (18–26°C). The disubstituted 1,3,4-oxadiazole derivatives were produced in excellent yields.     

Facile method for surface etching of silica aerogel monoliths

Degradation of three different endocrine disruptors (EDs) was thoroughly studied on prepared durable thin layers of titanium dioxide with an anatase crystalline structure. Specially constructed laboratory reactors bringing information on all individual processes (photolysis, photocatalysis, sorption) involved in decomposition of the studied EDs (17α-ethynylestradiol, bisphenol A and 4-nonylphenol) were applied. It was found that photolytic removal of EDs is the fastest degradation process; nevertheless, this method may be less effective regarding all indicators including toxicity. It was verified that individual degradation processes (photolysis and photocatalysis) showed a significantly different influence on toxicity of resulting solutions. During the photolytic process, EDs degradation caused increasing toxicity contrary to the photocatalytic process. Obtained results were corroborated by a mathematical model, which showed that a limitation step for photocatalysis is a sorption and for photolysis a toxicity of resulting products.

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