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Dr. Randa K. Gabr Prof. Dr. Takuji Hatakeyama Prof. Dr. Kazuhiro Takenaka Prof. Dr. Shinobu Takizawa Yoshihiro Okada Prof. Dr. Masaharu Nakamura Prof. Dr. Hiroaki Sasai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(29):9518-9525
The reaction pathway of an enantioselective 5‐endo‐trig‐type cyclization of 3‐alkenoic acids catalyzed by a chiral palladium–spiro‐bis(isoxazoline) complex, Pd–SPRIX, has been studied by density functional theory calculations. The most plausible pathway involves intramolecular nucleophilic attack of the carboxylate moiety on the C?C double bond activated by Pd–SPRIX and β‐H elimination from the resulting organopalladium intermediate. The enantioselectivity was determined in the cyclization step through the formation of a π‐olefin complex, in which one of the two enantiofaces of the olefin moiety was selected. The β‐H elimination occurs via a seven‐membered cyclic structure in which the acetate ligand plays a key role in lowering the activation barrier of the transition state. In the elimination step, the SPRIX ligand was found to behave as a monodentate ligand due to the hemilability of one of the isoxazoline units thereby facilitating the elimination. Natural population analysis of this pathway showed that the more weakly electron‐donating SPRIX ligand, compared with the bis(oxazoline) ligand, BOX, facilitated the formation of the π‐olefin complex intermediate, leading to a smaller overall activation energy and a higher reactivity of the Pd–SPRIX catalyst. 相似文献
105.
A modified technique of the self-absorption method has been developed and applied to natural mercury afterglows. A narrow light-emitting layer is produced inside an absorption tube by external pumping at the moment of measuring the afterglow. 相似文献
106.
Ken Okada Miyako Akiyoshi Atsumi Miyake Terushige Ogawa Mitsuo Nomura Takehiro Matsunaga 《Journal of Thermal Analysis and Calorimetry》2009,97(2):769-774
On January 21, 2003, an explosion occurred while ion exchange resin (IER) was being used to separate impurities from uranium
solution. To clarify the cause of the accident and go/no-go criteria of the explosion, elemental analysis of the IER, DSC
analysis, and SIKAREX analysis (a screening tool for runaway reactions) were performed. Finally, experiments on the same scale
as the accident were conducted in an explosion chamber. When HClO4 was added to IER-NO3, the IER violently exploded without any heating nor metal ions such as uranium. It was confirmed that the accident was caused
by an incorrect procedure in the chemical process. From the standpoint of explosion safety, IER-NO3 in particular should be kept away from perchloric acid in the laboratory. 相似文献
107.
Yutaka Nagasawa Ayako Watanabe Yoshito Ando Tadashi Okada 《Journal of Molecular Liquids》2001,90(1-3):295-302
We have studied femtosecond ground state recovery dynamics of phenol blue (PB) by pump-probe spectroscopy with a time resolution of 33 fs. Multiexponential decay with time constants extending from 300 fs to 10 ps were observed. Some low frequency intramolecular quantum beats were also observed. Solvent dependence of these decays and beats are discussed. 相似文献
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