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71.
Otera J Fujita Y Sakuta N Fujita M Fukuzumi S 《The Journal of organic chemistry》1996,61(9):2951-2962
Mechanism of Mukaiyama-Michael reaction of ketene silyl acetal has been discussed. The competition reaction employing various types of ketene silyl acetals reveals that those bearing more substituents at the beta-position react preferentially over less substituted ones. However, when ketene silyl acetals involve bulky siloxy and/or alkoxy group(s), less substituted compounds react preferentially. The Lewis acids play an important role in these reactions. Enhanced preference for the more sterically demanding Michael adducts is obtained with Bu(2)Sn(OTf)(2), SnCl(4), and Et(3)SiClO(4) in the former reaction while TiCl(4) gives the highest selectivity for the less sterically demanding products in the latter case. These results are interpreted in terms of alternative reaction mechanisms. The reaction of less bulky ketene silyl acetals are initiated by electron transfer from these compounds to a Lewis acid. On the other hand, bulkier ketene silyl acetals undergo a ubiquitous nucleophilic reaction. Such a mechanistic change is discussed based on a variety of experimental results as well as the semiempirical PM3 MO calculations. 相似文献
72.
Kenshu Fujiwara Masanori Kobayashi Fuyuki Yamamoto Yu-ichi Aki Mariko Kawamura Daisuke Awakura Seiji Amano Azusa Okano Akio Murai Hidetoshi Kawai Takanori Suzuki 《Tetrahedron letters》2005,46(30):5067-5069
The common left-half [C31-C33(OC1-C7)-C40] part of pectenotoxins has been synthesized convergently from the C31-C35, C36-C40, and C1-C7 parts. The C31-C35 part, prepared via a new route shorter than our previous route, was coupled with the C36-C40 part through reductive lithiation and addition reactions to give an adduct stereoselectively, which was converted to a cyclic acetal corresponding to the C31-C40 part. The left-half was synthesized by a three-step process including esterification of the C31-C40 part with the C1-C7 part. 相似文献
73.
[reaction: see text] A new class of molecular machine exhibits a hingelike motion upon photoirradiation. The motion (close and open) can be operated by alternate irradiation with UV and visible light. The trans/trans and cis/cis isomers are thermally stable at 40 degrees C, and the photochemical closure reaction (from trans/trans to cis/cis isomer) is dependent on the intensity of the light used because of the short-lived intermediate (trans/cis isomer). 相似文献
74.
Chromatographic separation of styrene-methyl methacrylate (MMA) copolymers depending on the chemical composition was studied using liquefied carbon dioxide as an adsorption promoting solvent, and tetrahydrofuran, chloroform containing ethanol as a desorption promoting solvent in the mobile phase and the column packed non-bonded silica gel by a solvent gradient method. With the increase of MMA content, the elution was retarded indicating that the typical normal-phase type of adsorption occurred. The effects of type of desorption solvents, molecular mass of sample, and column temperature on the elution were investigated. 相似文献
75.
Akihiko Ishii Masashi Saitoh Tetsuhiko Kawai Masami Murata Juzo Nakayama 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8-9):2025-2026
The reaction of isolable dithiirane 1-oxides with (Ph 3 P) 2 Pt( m 2 -C 2 H 4 ) provided the title complexes in high yields. 31 P NMR spectroscopy of the phosphine ligands of the complexes and x-ray crystallographic analysis of a complex were reported. 相似文献
76.
Sadayuki Mori Tetsuya Karita Koichi Komatsu Nobuyuki Sugita Terence S. M. Wan 《合成通讯》2013,43(9):1475-1482
Under high pressure conditions, fullerene C60 smoothly reacts with 2H-pyran-2-one to give a [4+2] cycloadduct, which can be reduced to an alcohol derivative. 相似文献
77.
78.
Green organogelators with a sulfide linkage and free amino groups were synthesized via phase transfer catalysis using a N-benzylcinchonidinium bromide catalyst. Their self-assemblies in various common solvents were examined. These compounds exhibit high gelation ability especially in aromatic and highly polar solvents with a low critical gelation of 0.1 wt %. The organogels were analyzed by 1H nuclear magnetic resonance (1H NMR) and Fourier transfer-infrared spectroscopies (FT-IR), and their phase transition temperatures were determined by differential scanning calorimetry. The homogeneity of the gel networks was examined by field emission scanning electron microscopy and transmission electron microscopy (TEM). A lamellar structure was also confirmed by X-ray diffraction analysis. The organogels were employed as soft-templates for the in situ generation of stable gold nanoparticles dispersed in the gel matrix, and the resulting GNP dispersions were studied by 1H NMR and UV–vis absorption. Transmission electron microscopy showed that GNPs assemble into a thin membrane-like structure. 相似文献
79.
Plasma-enhanced MOCVD in which metal-organic compounds are sublimated directly into the growth chamber is studied for the first time as a new low-temperature process for growing superconducting YBa2Cu3O--x thin films. Y(THD)3, Ba(THD)2, Cu(THD)2 and oxygen are used as metal sources and oxydizing agent. Emission spectroscopy reveals that activated metal-organic compounds and activated oxygen species are present during film growth. Superconducting YBa2Cu3O7-x films whose zero-resistivity temperature are 50 K and 82 K are grown at 550°C and 600°C. 相似文献
80.