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1.
Dr. Christopher R. Opie Dr. Hidetoshi Noda Prof. Dr. Masakatsu Shibasaki Dr. Naoya Kumagai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4648-4653
The B3NO2 six-membered heterocycle (1,3-dioxa-5-aza-2,4,6-triborinane=DATB), comprising three different non-carbon period 2 elements, has been recently demonstrated to be a powerful catalyst for dehydrative condensation of carboxylic acids and amines. The tedious synthesis of DATB, however, has significantly diminished its utility as a catalyst, and thus the inherent chemical properties of the ring system have remained virtually unexplored. Here, a general and facile synthetic strategy that harnesses a pyrimidine-containing scaffold for the reliable installation of boron atoms is disclosed, giving rise to a series of Pym-DATBs from inexpensive materials in a modular fashion. The identification of a soluble Pym-DATB derivative allowed for the investigation of the dynamic nature of the B3NO2 ring system, revealing differential ring-closing and -opening behaviors depending on the medium. Readily accessible Pym-DATBs proved their utility as efficient catalysts for dehydrative amidation with broad substrate scope and functional-group tolerance, offering a general and practical catalytic alternative to reagent-driven amidation. 相似文献
2.
Hidetoshi Shimodaira 《Annals of the Institute of Statistical Mathematics》1997,49(3):395-410
The asymptotic error probability of Linhart's model selection test isevaluated, and compared with the nominal significance level. We examine thecase where the expected discrepancies of the candidate models from the truemodel are asymptotically equal. The local alternatives method is employed inthe limiting operation of the asymptotic evaluation. Although the errorprobability under the null hypothesis is actually shown to be equal to orless than the level for most situations, intolerable violations of the errorcontrol are observed for nested models: It is often erroneously concludedthat the smaller model is significantly better than the larger model. Toprevent this violation, a modification of Linhart's test statistic isproposed. The effectiveness of the proposed test is confirmed throughtheoretical analysis and numerical simulations. 相似文献
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Yan Yin Otoo Yamada Shunsuke Hayashi Kazuhiro Tanaka Hidetoshi Kita Ken‐Ichi Okamoto 《Journal of polymer science. Part A, Polymer chemistry》2006,44(12):3751-3762
A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm?1 at 50% relative humidity. In a single H2/O2 fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006 相似文献
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Katsunori Nishimura Rie Hidaka Fumitoshi Hirayama Hidetoshi Arima Kaneto Uekama 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(1-2):85-88
Geometries, electronic properties and NMR-shielding of cucurbit[5]uril, decamethylcucurbit[5]uril, cucurbit[6]uril, cucurbit[7]uril,
and cucurbit[8]uril are investigated with DFT calculations. All molecules are highly symmetrical with a distinct geometric
flexibility. In addition with a characteristic partial charge distribution these findings account for their chemical complex
building ability. 相似文献
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Takanori Suzuki Tomohiro Iwai Eisuke Ohta Hidetoshi Kawai Kenshu Fujiwara 《Tetrahedron letters》2007,48(20):3599-3603
Huge CD amplitude (A = +538) was attained by diastereomeric preference (50% de) for the title dication with two bis[4-(R)-sec-butoxyphenyl]methylium units in benzene at 23 °C. Intramolecular π-π stacking is the origin for effective transmission of point chirality to axial chirality to attain the chiroptical enhancement of 400-times. Thanks to the strong CD signaling, chiroptical changes upon electrolysis could be readily detected, thus realizing a new class of electrochiroptical response systems. Chiroptical properties could also be modified by solvent polarity. 相似文献
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Esters of sulphur-containing 5- and 6-membered heterocycles, tetrahydro-3- and 4-thiopyranol and their 3- and 4-methyl, phenyl derivatives, and tetrahydro-2-thiophenemethanol, were synthesized. The solvolysis of β-thioesters in 80% aqueous acetone resulted in strong transannular S-participation and the products of solvolysis substantiated formation of bicyclic episulphonium ion intermediates. Such participation is considered to be present even in a tertiary system. On the other hand, γ-thioesters were solvolysed without any transannular S-participation, 相似文献