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1.
2-Isopropylbenzimidazole and 2-methylbenzimidazole have been found to be effective bulky proton sources for stereoselective protonation of chiral enolate anions. 2-Isopropylbenzimidazole worked in the stereoselective protonation of the Birch reduction of chiral α,β-unsaturated imides. On the other hand, 2-methylbenzimidazole was found to be the best protonation reagent in the isomerization reaction of α,β-unsaturated imide into β,γ-unsaturated imide. The Birch reduction using 2-isopropylbenzimidazole realized a concise and stereoselective synthesis of δ-lactone 14, a sex pheromone of Macrocentrus grandii, while the isomerization reaction using 2-methylbenzimidazole was employed in the highly stereoselective synthesis of the γ-lactone intermediate in the synthesis of depsipeptide antibiotics. These bulky proton sources would be powerful tools to achieve a concise synthesis of natural products. 相似文献
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A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State 下载免费PDF全文
Dr. Daisuke Sakamaki Soichiro Yano Toshiyuki Kobashi Prof. Dr. Shu Seki Dr. Takuya Kurahashi Prof. Dr. Seijiro Matsubara Dr. Akihiro Ito Prof. Dr. Kazuyoshi Tanaka 《Angewandte Chemie (International ed. in English)》2015,54(28):8267-8270
Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual C? N bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor. 相似文献
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Naoki Yoneda Yukihiro Fukata Dr. Keisuke Asano Prof. Dr. Seijiro Matsubara 《Angewandte Chemie (International ed. in English)》2015,54(51):15497-15500
Chiral spiroketal skeletons are found as core structures in a range of bioactive compounds. These natural compounds and their analogues have attracted much attention in the field of drug discovery. However, methods for their enantioselective construction are limited, and easily available optically active spiroketals are rare. We demonstrate a novel catalytic asymmetric synthesis of spiroketal compounds that proceeds through an intramolecular hemiacetalization/oxy‐Michael addition cascade mediated by a bifunctional aminothiourea catalyst. This results in spiroketal structures through the relay formation of contiguous oxacycles, in which multipoint recognition by the catalyst through hydrogen bonding imparts high enantioselectivity. This method offers facile access to spiroketal frameworks bearing an alkyl group at the 2‐position, which are prevalent in insect pheromones. Optically active (2S,5S)‐chalcogran, a pheromone of the six‐spined spruce bark beetle, and an azide derivative could be readily synthesized from the bicyclic reaction product. 相似文献
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Lingling Wang Yilan Jiang Yi Zhou Ruikai Shi Fumio Hosokawa Osamu Terasaki Qing Zhang 《Particle & Particle Systems Characterization》2023,40(1):2200122
It has become very important to study and find optimal conditions for imaging electron-beam (e-beam) sensitive materials in scanning transmission electron microscopy under low electron-dose with high signal-to-noise ratio (SNR). Convergence and collection angles and electron-probe current are essential parameters. However, these parameters have rarely been discussed in a systematic way. In this paper, the illumination and collection conditions are optimized according to the resolution requirement of different materials by adjusting the condenser and intermediate lenses in a commercial transmission electron microscope. To demonstrate the significance of optimizing these parameters, two examples, zeolite MFI and metal–organic framework (MOF) MIL-101, are taken among the sensitive materials, with the most important electron incidences along the [010] and <110> directions, respectively. High SNR atomic resolution images of MFI are obtained with e-beam current as low as 0.50 pA, reaching information transfer for reflection up to 18 0 2 corresponding to d-spacing of 0.11 nm, close to the resolution limit of 0.098 nm from resolvable diffraction limit. MOF MIL-101 is characterized under an even lower e-beam 0.2 pA to avoid severe beam damage. High-quality annular dark and bright field images are obtained, which proves the wide applicability of this method on more e-beam sensitive materials. 相似文献
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Recently Thoroddsen and Van Atta (1992, Phys. Fluids A4, 2592) showed that Kolmogorov's refined similarity hypothesis (1962, J. Fluid Mech. 13, 77; 82) is supported by experimental data from a wind-tunnel study of a cylinder wake, at Reλ of 550. We show here that the probability density of the Kolmogorov similarity variable approaches a Gaussian distribution. The data also suggest that it may obey an even more demanding conditional similarity, which leads to important conclusions regarding the scaling exponents. 相似文献
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Rei Tomifuji Prof. Takuya Kurahashi Prof. Seijiro Matsubara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(38):8987-8991
The development and use of a multiple-activation catalyst with ion-paired Lewis acid and Brønsted acid in an asymmetric aza-Diels–Alder reaction of simple dienes (non-Danishefsky-type electron-rich dienes) was achieved by utilizing the [FeBr2]+[FeBr4]− combination prepared in situ from FeBr3 and chiral phosphoric acid. Synergistic effects of the highly active ion-paired Lewis acid [FeBr2]+[FeBr4]− and a chiral Brønsted acid are important for promoting the reaction with high turnover frequency and high enantioselectivity. The multiple-activation catalyst system was confirmed using synchrotron-based X-ray absorption fine structure measurements, and theoretical studies. This study reveals that the developed catalyst promoted the reaction not only by the interaction offered by the ion-paired Lewis acid and the Brønsted acid but also noncovalent interactions. 相似文献
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A Doping Technique that Suppresses Undesirable H2 Evolution Derived from Overall Water Splitting in the Highly Selective Photocatalytic Conversion of CO2 in and by Water 下载免费PDF全文
Prof. Dr. Kentaro Teramura Zheng Wang Dr. Saburo Hosokawa Prof. Dr. Yoshihisa Sakata Prof. Dr. Tsunehiro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):9906-9909
Photocatalytic conversion of CO2 to reduction products, such as CO, HCOOH, HCHO, CH3OH, and CH4, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga2O3 photocatalysts exhibit high conversion of CO2. Doping of Zn species into Ga2O3 suppresses the H2 evolution derived from overall water splitting and, consequently, Zn‐doped, Ag‐modified Ga2O3 exhibits higher selectivity toward CO evolution than bare, Ag‐modified Ga2O3. We observed stoichiometric amounts of evolved O2 together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO2 introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO2 on the catalyst surface. 相似文献