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71.
Ralf Otte Roland Fröhlich Shuichi Nakamura Takeshi Toru Dieter Hoppe 《Tetrahedron letters》2007,48(49):8636-8642
The enantio- and diastereoselective synthesis of allenyl aryl sulfides by asymmetric lithiation of 2-alkynyl (2-hetero)aryl sulfides is described. A dynamic thermodynamic resolution by selective crystallization of the intermediate lithium complexes derived from deprotonation, applying a bis(oxazoline) ligand, was achieved to give enantioselectivities up to 85% ee. Subsequent stereospecific nickel-catalyzed cross-coupling reactions with arylzinc reagents established a versatile access to threefold carbon-substituted allenes. 相似文献
72.
Tsutomu Yokozawa Jun Takagi Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1989,27(1):291-299
Spontaneous copolymerization of cyclic ketene acetal, 2-methylene-4-phenyl-1,3-dioxolane ( I ) with common electrophilic vinyl monomers, such as methyl α-cyanoacrylate (MCA), acrylonitrile (AN), and methyl methacrylate (MMA) were investigated to further explore zwitterion polymerization method with cyclic ketene acetals. In the reaction of I with MCA and AN, spontaneous copolymerization took place at ambient temperature. The copolymers of I with MCA gave low molecular weight polymers, but copolymers obtained with I and AN were high molecular weight polymers. In the reaction of I and MMA, high molecular weight copolymer was obtained only at temperatures above 80°C. Thus, obtained polymers were not the alternating copolymers and possessed high I content in all the cases. From the above results, macrozwitterionic mechanism was suggested as discussed. 相似文献
73.
Tomooka K Komine N Fujiki D Nakai T Yanagitsuru S 《Journal of the American Chemical Society》2005,127(35):12182-12183
Remarkably stable planar chirality was found in a nine-membered diallylic cyclic ether. Enantiomerically enriched ether was prepared by a kinetic resolution of a racemic one, which is valuable as a novel type of chiral building block. 相似文献
74.
Satoshi ObikaJyun-ichi Andoh Mayumi OnodaOsamu Nakagawa Akiko HirotoTomomi Sugimoto Takeshi Imanishi 《Tetrahedron letters》2003,44(28):5267-5270
A novel bridged nucleic acid monomer, 3′-amino-3′-deoxy-5-methyl-3′-N,4′-C-methyleneuridine, was successfully synthesized via a useful and convenient azetidine ring formation under Staudinger's conditions. A 1H NMR experiment and a PM3 calculation revealed that the sugar moiety of the novel bridged nucleic acid monomer, 3′-amino-3′,4′-BNA, was restricted to S-type conformation. 相似文献
75.
Takeshi Takeda Tomohiro ShonoKenji Ito Hironori SasakiAkira Tsubouchi 《Tetrahedron letters》2003,44(43):7897-7900
Aldehydes, ketones, esters and lactones are transformed into enol ethers or 1,2-dialkoxy-1-alkenes by treatment with organotitanium species prepared from alkoxymethyl chlorides and a titanocene(II) complex. 相似文献
76.
Terutaka Watanabe Takeshi Wada Masaaki Takehisa Sueo Machi 《Journal of polymer science. Part A, Polymer chemistry》1974,12(8):1619-1628
The heterogeneous polymerization of ethylene initiated by radiation in tert-butyl alcohol was studied. The polymerization was carried out in a 100-ml reactor at 25–100°C and pressures of 200–300 kg/cm2 in the presence of 50 ml of tert-butyl alcohol containing 7 wt-% water. The amounts of polymerized monomer, the average molecular weight of polymer formed, and the molecular weight distribution of polymer were measured at various stages of reaction and at various temperatures. The molecular weight distribution was found to be very much dependent on the reaction time and temperature. For the polymer formed at 50–60°C in the very early stages of reaction, the molecular weight distribution is unimodal, and in the intermediate stage a shoulder appears at a molecular weight higher than the first peak which increases as the polymerization proceeds; eventually a bimodal curve is formed. The bimodal distribution curves were analyzed to determine the fractions and average molecular weights of the each peak. On the basis of these data for the molecular weight distribution and kinetic behavior, a new scheme for the heterogeneous polymerization is proposed which indicates that the polymerization proceeds via propagating radicals in two different physical states, namely, loose and rigid states. 相似文献
77.
The C-12˜C-17 segment
of (+)-aplasmomycin (
) was synthesized stereoselectively starting from (−)-malic acid based on the stereoselective ketone reduction. 相似文献
78.
Kentaro Ageishi Takeshi Endo Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1981,19(5):1085-1090
The behavior of viologen polymer (P-V2+) as an electron transfer catalyst in the reaction of hydrogen generation was studied. In the photoirradiation system, which contains triethanolamine (TEA), Ru(bpy)3+3, and P-V2+, the amount of hydrogen evolution was less than methyl viologen (MV2+); P-V2+, however, was more effective in sodium dithionite as the electron donor and showed higher initial rates than MV2+. 相似文献
79.
Oikawa H Nakamura K Toshima H Toyomasu T Sassa T 《Journal of the American Chemical Society》2002,124(31):9145-9153
To examine the mechanism of the cyclization reaction catalyzed by aphidicolan-16beta-ol synthase (ACS), which is a key enzyme in the biosynthesis of diterpene aphidicolin, a specific inhibitor of DNA polymerase alpha, skeletal rearrangement of 2a and biomimetic cyclization of 4b were employed. The structures of the reaction products, which reflect penultimate cation intermediates, allowed us to propose a detailed reaction pathway for the Lewis acid-catalyzed cyclizations and rearrangements. Isolation of these products in an aphidicolin-producing fungus led us to speculate that the mechanism of the ACS-catalyzed cyclization reaction is the same as that of a nonenzymatic reaction. Ab initio calculations of the acid-catalyzed reaction intermediates and the transition states indicate that the overall reaction catalyzed by ACS is an exothermic process though the reaction proceeds via an energetically disfavored secondary cation-like transition state. In conjunction with the solvent effect in the acid-catalyzed reactions, this indicates that the actual role of ACS is to provide a template which enforces conformations of the intermediate cations leading to the productive cyclization although it has been believed that the cation-pi interaction between cation intermediates and aromatic amino acid residues in the active site is important for the enzymatic catalysis. This study provided important information on the role of various cationic species, especially secondary cation-like structures, in both nonenzymatic and enzymatic reactions. 相似文献
80.
Yoshiaki Sugihara Naoto Inai Masayasu Taki Thomas Baumgartner Ryosuke Kawakami Takashi Saitou Takeshi Imamura Takeshi Yanai Shigehiro Yamaguchi 《Chemical science》2021,12(18):6333
The use of donor–π–acceptor (D–π–A) skeletons is an effective strategy for the design of fluorophores with red-shifted emission. In particular, the use of amino and boryl moieties as the electron-donating and -accepting groups, respectively, can produce dyes that exhibit high fluorescence and solvatochromism. Herein, we introduce a dithienophosphole P-oxide scaffold as an acceptor–spacer to produce a boryl- and amino-substituted donor–acceptor–acceptor (D–A–A) π-system. The thus obtained fluorophores exhibit emission in the near-infrared (NIR) region, while maintaining high fluorescence quantum yields even in polar solvents (e.g. λem = 704 nm and ΦF = 0.69 in CH3CN). A comparison of these compounds with their formyl- or cyano-substituted counterparts demonstrated the importance of the boryl group for generating intense emission. The differences among these electron-accepting substituents were examined in detail using theoretical calculations, which revealed the crucial role of the boryl group in lowering the nonradiative decay rate constant by decreasing the non-adiabatic coupling in the internal conversion process. The D–A–A framework was further fine-tuned to improve the photostability. One of these D–A–A dyes was successfully used in bioimaging to visualize the blood vessels of Japanese medaka larvae and mouse brain.Combination of electron-accepting diarylboryl terminal groups and dithienophosphole oxide spacers with electron-donating triarylamine moieties produces donor–acceptor–acceptor type π-systems, which exhibit emissions in the near-infrared region. 相似文献