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21.
Sekino E Kumamoto T Tanaka T Ikeda T Ishikawa T 《The Journal of organic chemistry》2004,69(8):2760-2767
(-)-Quinine-catalyzed intramolecular oxo-Michael addition (IMA) of 7-hydroxy-5-methoxy-8-tigloylcoumarins was developed for the enantioselective construction of 2,3-dimethyl-4-chromanone systems in the context of the asymmetric synthesis of anti-HIV-1 active Calophyllum coumarins. Combination of the IMA and MgI(2)-assisted demethylation of the 5-methoxy group along with isomerization of the formed chromanone systems as key steps successfully led to the concise synthesis of (+)-inophyllum B and (+)-calanolide A, possible candidates for AIDS drugs. Further examination of the asymmetric IMA with cinchona alkaloids lacking a methoxy group on the quinoline skeleton suggested the influence of the methoxy substituent on stereoselectivity at the stereogenic centers of the chromanone systems. 相似文献
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Seiichi Nakamura Jun Inagaki Tomohiro Sugimoto Yasuyuki Ura Shunichi Hashimoto 《Tetrahedron》2002,58(52):10375-10386
An efficient, highly stereoselective synthesis of the C10–C31 (BCDEF ring) portion of pinnatoxin A has been achieved utilizing tandem double hemiketal formation/intramolecular hetero-Michael addition to construct the 6,5,6-dispiroketal (BCD ring) system and subsequent intramolecular ketalization to form the 5,6-bicycloketal (EF ring) system as key steps. 相似文献
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Chi Feng Tomohiro Seki Shunichi Sakamoto Toshiyuki Sasaki Satoshi Takamizawa Hajime Ito 《Chemical science》2022,13(33):9544
Shape-memory materials can be mechanically deformed and subsequently reverse the deformation upon changing the temperature. Shape-memory materials have attracted considerable attention for basic research and industrial applications, and polymer and alloy shape-memory materials have been well studied; however, it is formidably challenging to develop functional shape-memory materials, such as materials with multi-stage and anisotropic shape changes and shape changes accompanied by changes in color and light emission. Here, we found a reversible multi-stage shape-changing effect after mechanical deformation in a molecular crystal induced by multi-step thermal phase transitions with reversible shape changes and luminescence-color changes. Using single-crystal structure and thermal analyses as well as mechanical property measurements, we found that the reversible multi-stage shape-changing effect was achieved by a combination of a twinning deformation and multi-step thermal phase transitions. The changes in the crystal shape and luminescence suggest novel strategies for imparting known shape-memory materials with additional functionalities.A reversible multi-stage shape-changing material based on an organic crystalline material is presented. Intriguingly, the interconversion among the three different shapes is accompanied by changes of the luminescence color. 相似文献
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Dr. Adam A. Sobczuk Dr. Youichi Tsuchiya Dr. Tomohiro Shiraki Dr. Shun‐ichi Tamaru Prof. Seiji Shinkai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):2832-2838
A unique class of oligothiophene‐based organogelator bearing two crown ethers at both ends was synthesized. This compound could gelatinize several organic solvents, forming one‐dimensional fibrous aggregates. From the observation of circular dichroism, it was confirmed that the helical handedness of the fibrous assembly is controllable by the chirality of 1,2bisammonium guests, thus suggesting that one guest molecule bridges two gelator molecules through the crown–ammonium interaction. Interestingly, we have found that such chirality is created by thermal gelation, whereas it disappears by thixotropic gelation. The new finding implies that the present organogel system is applicable as a reversible switching memory device, featuring memory creation by a heat mode and memory erasing by a mechanical mode. 相似文献
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Eric M. Yezdimer Tomohiro Umemoto Hiroshi Yamada Satoshi Makino Ikuo Tooyama 《Applied biochemistry and biotechnology》2013,170(5):1138-1150
The potential utility of an imaging agent for the detection of hepatic copper was investigated in a Wilson’s disease animal model. Solid-phase peptide synthesis was used to construct an imaging agent which consisted of a copper-binding moiety, taken from the prion protein, and a gamma ray-emitting indium radiolabel. Long–Evans Cinnamon (LEC) rats were used for the Wilson’s disease animal model. Our evaluation methodology consisted of administering the indium-labeled agent to both LEC and genetically healthy Long–Evans (LE) cohorts via a tail vein injection and following the pharmacokinetics with single-photon emission computed tomography (SPECT) over the course of an hour. The animals were then sacrificed and their livers necropsied. An additional control agent, lacking the copper-binding moiety, was used to gauge whether any change in the hepatic uptake might be caused by other physiological differences between the two animal models. LEC rats injected with the indium-labeled agent had roughly double the amount of hepatic radioactivity as compared to the healthy control animals. The control agent, without the copper-binding moiety, displayed a hepatic signal similar to that of the control LE animals. Additional intraperitoneal spiking with CuSO4 in C57BL/6 mice also found that the pharmacokinetics of the indium-labeled, prion-based imaging agent is profoundly altered by exposure to in vivo pools of extracellular copper. The described SPECT application with this compound represented a significant improvement over a previous MRI application using the same base peptide sequence. 相似文献
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Prof. Takanori Suzuki Yuto Sakano Dr. Tomohiro Iwai Dr. Shinichi Iwashita Dr. Youhei Miura Dr. Ryo Katoono Prof. Hidetoshi Kawai Prof. Kenshu Fujiwara Prof. Yasushi Tsuji Prof. Takanori Fukushima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(1):117-123
When two benzene rings are fused to a tetraaryl‐o‐quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron‐donating alkoxy groups, 1 undergo reversible two‐electron oxidation to 2 2+, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec‐butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b 2+ and 2 c 2+, which represents an efficient method for enhancing circular‐dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X‐ray analysis of dication 2 2+ revealed π–π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response. 相似文献