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91.
Dr. Toshifumi Dohi Nobutaka Yamaoka Shota Nakamura Kohei Sumida Koji Morimoto Prof. Dr. Yasuyuki Kita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2067-2075
We have successfully established an efficient route to the core structure of donor–acceptor head‐to‐tail (H–T)‐linked regioregular oligothiophenes, which includes the following key synthetic steps, that is, hypervalent iodine induced direct and regioselective coupling of thiophenes and the use of the obtained bithiophenes as excellent coupling substrates for the Suzuki and Stille couplings. The versatility of this new approach is highlighted in the dramatic improvement of the yield (ca. 59 % overall yield) of MK‐2, a high‐performance organic dye, for photovoltaic applications. 相似文献
92.
Ken Takaki Toshifumi FujiiHosei Yonemitsu Makoto FujiwaraKimihiro Komeyama Hiroto Yoshida 《Tetrahedron letters》2012,53(31):3974-3976
Hetero-Diels-Alder reaction of α-hydroxy-o-quinodimethanes photochemically generated from o-tolualdehydes with trifluoromethyl ketones gave a mixture of hemiacetals and hydroxyaldehydes in fairly good yields. Their subsequent oxidation with PCC provided 1-isochromanones as formal oxidative [4+2] cycloaddition products. In contrast, similar reaction of aromatic ketones such as o-methylbenzophenone, 1-indanone, and α-tetralone gave exclusively the corresponding ketones having (trifluoromethyl)methylol groups at the o-position. 相似文献
93.
94.
We developed a new one-pot reaction of phenolic acids to afford the corresponding esters and amides through acyl-protected and activated phenolic acid intermediates. The simultaneous protection/activation of phenolic acids with alkylchloroformates proceeded readily in the presence of DMAP at room temperature; subsequent addition of alcohols or amines afforded the corresponding esters or amides. The use of iso-butyloxycarbonyl as the protecting and activating group in the one-pot reactions afforded phenolic esters or amides in 91% average yield. As a practical example of this convenient synthesis, caffeic acid phenethyl ester (CAPE) was readily synthesized from commercially available caffeic acid and phenethyl alcohol in 95% yield, and an isotopomer of CAPE, [3,10-13C2]CAPE, was synthesized in 91% yield from [3-13C]caffeic acid and 2-[1-13C]phenethyl alcohol. This method may be useful for the convenient esterification and amidation of diverse phenolic acids. 相似文献
95.
Chemical Synthesis of O‐Glycosylated Human Interleukin‐2 by the Reverse Polarity Protection Strategy 下载免费PDF全文
Dr. Yuya Asahina Shinobu Komiya Ami Ohagi Rina Fujimoto Dr. Hiroko Tamagaki Katsuhiro Nakagawa Dr. Takashi Sato Prof. Dr. Shizuo Akira Prof. Dr. Toshifumi Takao Dr. Akira Ishii Prof. Dr. Yoshiaki Nakahara Prof. Dr. Hironobu Hojo 《Angewandte Chemie (International ed. in English)》2015,54(28):8226-8230
The chemical synthesis of human interleukin‐2 (IL‐2) , having a core 1 sugar, by a ligation method is reported. Although IL‐2 is a globular glycoprotein, its C‐terminal region, in particular (99‐133), is extremely insoluble when synthesized by solid‐phase method. To overcome this problem, the side‐chain carboxylic acid of the Glu residues was protected by a picolyl ester, thus reversing its polarity from negative to positive. This reverse polarity protection significantly increased the isoelectric point of the peptide segment and made it positive under acidic conditions and facilitated the purification. An efficient method to prepare the prolyl peptide thioester required for the synthesis of the (28‐65) segment was also developed. These efforts resulted in the total synthesis of the glycosylated IL‐2 having full biological activity. 相似文献
96.
Ryosuke Sakai Takafumi Yonekawa Issei Otsuka Ryohei Kakuchi Toshifumi Satoh Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2010,48(5):1197-1206
Diacetylene monomers with respective lengths of the oxyethylene chains were cyclopolymerized with a rhodium catalyst to produce novel poly(phenylacetylene)s bearing a different cavity size of the chiral crown ether in the repeating units ( 2a – c ). In the circular dichroism spectra of the resulting polymers, characteristic Cotton effects were observed in the range from 350 to 500 nm corresponding to the absorption of the conjugated polymer backbone, indicating that the polymers possessed a helical structure with an excess single screw sense induced by the covalently bonded binaphthyl units. The host–guest complexation of 2a – c with achiral guests produced a chiroptical change based on the fluctuation in the main chain conformation. The behavior of the complexation‐induced chiroptical change was essentially dictated by the cavity size of the binaphthocrown ether units. Additionally, a chirality‐responsive helicity change was observed in the case of the complexation of 2a – c with chiral guests, which also depended on the crown ether size. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1197–1206, 2010 相似文献
97.
Kassai H Satomi Y Fukada Y Takao T 《Rapid communications in mass spectrometry : RCM》2005,19(2):269-274
Protein isoprenylation, an important post-translational modification with a lipid, involves the selective attachment of two types of isoprenoids, farnesyl (C15) and geranylgeranyl (C20). The isoprenoid is linked via a thioether bond to the C-terminal cysteine residue of a variety of cellular proteins, including the heterotrimeric G protein gamma-subunits. One member of the G protein family, transducin (Talpha/Tbetagamma), plays a central role in visual transduction, and the structure-function relationship has been extensively studied with purified proteins, predominantly with bovine transducin that was shown to be farnesylated at the C-terminal cysteine residue of the gamma-subunit (Tgamma). We report here the structure of the C-terminal modification of mouse Tgamma, which has not yet been elucidated owing to the low amount of protein that can be isolated from the mouse retina. Electrospray ionization mass spectrometry (ESI-MS) of the high-performance liquid chromatography (HPLC)-purified Tgamma was in good agreement with the calculated mass of the farnesylated and methylated form of mouse Tgamma (Pro1-Cys70). A 'top-down' analysis of intact Tgamma using an ESI hybrid quadrupole time-of-flight (TOF) tandem mass spectrometer provided isoprenyl-specific ions that were observed to produce ions separated by 204 Da from the conventional (unmodified) precursor ion or the C-terminal sequence ions. Such characteristic fragmentation on an isoprenoid observed in top-down analysis could be useful in general for determining the type of isoprenylation as well as probing the site of modification in the protein sequence. 相似文献
98.
We report the synthesis of various thiophene/phenylene co‐oligomers with a total number of thiophene and benzene (phenylene) rings of 6 to 8. These compounds include a phenyl‐capped sexithiophene, a thienyl‐capped quaterphenylene, as well as block and alternating co‐oligomers. The synthesis is based on either the Suzuki coupling reaction or the direct dimerization coupling. The latter method produces symmetric molecules with an even total ring number. These reaction schemes enabled us to obtain the target compounds in high quality. Although the resulting materials are difficult to dissolve in organic solvents and therefore difficult to identify by usual 1H nmr spectroscopy, they have successfully been identified through Fourier‐transform ir spectroscopy. The specific group frequencies of ring‐stretching and out‐of‐plane deformation modes are characteristic of the substitution pattern of the individual thiophene and benzene rings. 相似文献
99.
Tomoko Imai Kohei Hayakawa Toshifumi Satoh Harumi Kaga Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3443-3448
Enantiomer‐selective polymerization of (RS)‐(phenoxymethyl)thiirane (RS‐ 1 ) was carried out with ZnEt2/L ‐α‐amino acid as an initiator system, and the effect of the initiator system on the enantiomer selectivity was examined with various amino acids. All polymerizations heterogeneously proceeded, and every initiating system was effective in producing optically active polymers. For the polymerization of RS‐ 1 with diethylzinc (ZnEt2)/L ‐leucine (1/1), the conversion was 43.7% in 12 days, and the number‐average molecular weight of the polymer was 18,000. The enantiomer selectivity was maximum when the molar ratio of the two components in the ZnEt2/L ‐α‐amino acid system was 1:1. When the ZnEt2/L ‐leucine (1/1) system was used in the polymerization, the best result was obtained with an enantiomer‐selectivity value of 5.36. During the polymerization, the S enantiomer was preferentially consumed, and the isotactic‐rich polymer was enriched in the S configurational units produced. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3443–3448, 2002 相似文献
100.
Polylactide (PLA)-grafted dextran (Dex-graft-PLA) of various contents of sugar units was synthesized by anionic polymerization of L-lactide (L-LA) using the alkoxide of partially trimethylsilylated dextran (TMSDex) and subsequently removing the trimethylsilyl (TMS) groups. The copolymer showed different solubility from L-LA homopolymer with increasing the content of sugar units. We prepared bovine serum albumin (BSA)-loaded microspheres (MS)s according to a water-in-oil-in-water emulsion-solvent evaporation/extraction method using methylene chloride/DMSO as an organic cosolvent. MSs prepared from Dex-graft-PLA [MS(Dex-graft-PLA)s] exhibited higher loading efficiency of BSA than MSs prepared from PLLA [MS(PLLA)s]. The in vitro release rate of BSA from MS(Dex-graft-PLA) was faster than that from MS(PLLA). BSA released from MS(Dex-graft-PLA) maintained the secondary structure of native BSA to a great extent, compared with BSA released from MS(PLLA). 相似文献