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21.
Stereodivergent Synthesis and Stereochemical Reassignment of the C79–C104 Fragment of Symbiodinolide 下载免费PDF全文
Prof. Dr. Hiroyoshi Takamura Takayuki Fujiwara Yohei Kawakubo Prof. Dr. Isao Kadota Prof. Dr. Daisuke Uemura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):1984-1996
We have synthesized eight possible diastereoisomers 3 a – h of the C79–C97 fragment of symbiodinolide ( 1 ) in a stereodivergent manner by utilizing a dithiane addition to the aldehyde as a key step. Comparison of the 13C NMR chemical shifts of the natural product 1 and the synthetic products 3 a – h indicated that the relative stereostructure of this fragment in symbiodinolide ( 1 ) is that represented in 3 a or f . We have stereodivergently synthesized eight possible diastereoisomers of the C94–C104 fragment 4 a – h , and we have compared their 13C NMR chemical shifts with those of the natural product, which established the relative stereochemistry of this fragment to be that described in diastereoisomers 4 a or e . By combining the stereostructural outcomes of the C79–C97 and C94–C104 fragments, we have proposed four candidate compounds of the C79–C104 fragment 2 a – d . We also synthesized diastereoisomers 2 a and b ( 2 a in the preceding article; Chem. Eur. J. 2015 , DOI: 10.1002/chem.201503880) by a Julia–Kocienski olefination and diastereoisomers 2 c and d by a Wittig reaction. By comparing the 13C NMR chemical shifts of natural symbiodinolide ( 1 ) with those of the synthetic products 2 a – d , we have reassigned the stereostructure of the C79–C104 fragment of natural product 1 to be that depicted in diastereoisomer 2 b . 相似文献
22.
The labeling of oligo- and polynucleotides with fluorescent probes is an important technique for the analysis of DNAs and RNAs. The effect of duplex formation with complementary oligo-DNA on the quenching behavior of two fluorescent chromophores (eosin, Eo and tetramethylrhodamine, TMR) attached to the 5′-terminal of various 10mer oligo-DNAs was investigated and the dependence of the quenching on DNA base sequence is discussed. We found that guanine residues played a major role in the quenching of the fluorescence of the chromophores. Guanine residues on the complementary DNA near the chromophores, in particular, had a significant influence on the quenching. 相似文献
23.
Yusuke Fukahori Yohei Takayama Takuya Imaoka Dr. Osamu Iwamoto Prof. Dr. Kazuo Nagasawa 《化学:亚洲杂志》2013,8(1):244-250
We present a diastereoselective synthesis of disubstituted cyclopentane 8 having a nitrogen‐containing quaternary carbon center, which is found in axinellamine A ( 5 ) and related compounds. During this work, we found that the 1,3‐dipolar cycloaddition product 24 immediately underwent intramolecular redox reaction at the newly formed morpholin‐2‐one moiety, thus affording disubstituted cyclopentane containing a tertiary amine ( 9 ) stereoselectively in good yield. The amine 9 was successfully converted into guanidine 31 , which corresponds to 8 , through iminium cation–enamine isomerization. 相似文献
24.
Adsorption and photochemical behaviors of the novel cationic xanthene derivative on the clay surface
Yuta Ohtani Yohei Ishida Yuka Ando Hiroshi Tachibana Tetsuya Shimada Shinsuke Takagi 《Tetrahedron letters》2014
Novel tetra-cationic xanthene derivative (Flu) was synthesized. Its adsorption and photochemical behaviors on the clay surface were investigated. Fluorescence quantum yield (?f) and fluorescence lifetime were 0.50 and 2.9 ns for Flu/clay complex. ?f of Flu was enough high (>0.1) even at high density conditions (0.080 molecules nm−2). It is supposed that the strong interaction between clay and Flu by the ‘Size-Matching Effect’ realizes the highly emissive clay complexes at high density adsorption condition by a suppression of a molecular aggregation, which tends to decrease the photochemical activity. 相似文献
25.
Yohei Saito Atsushi Mizokami Kouji Izumi Renato Naito Masuo Goto Kyoko Nakagawa-Goto 《Molecules (Basel, Switzerland)》2021,26(9)
α-Trifluoromethyl chalcones were prepared and evaluated for their antiproliferative activities against androgen-independent prostate cancer cell lines as well as five additional types of human tumor cell lines. The most potent chalcone 5 showed superior antitumor activity in vivo with both oral and intraperitoneal administration at 3 mg/kg. Cell-based mechanism of action studies demonstrated that 5 induced cell accumulation at sub-G1 and G2/M phases without interfering with microtubule polymerization. Furthermore, several cancer cell growth-related proteins were identified by using chalcone 5 as a bait for the affinity purification of binding proteins. 相似文献
26.
T. Izumikawa D. Shinojima S. Takahashi M. Mihara K. Matsuta M. Fukuda T. Ohtsubo S. Ohya T. Minamisono 《Hyperfine Interactions》2007,178(1-3):79-82
The β-NMR of the probe atom 12B implanted in In-doped germanium was measured as a function of temperature. As a result, three resonances were observed: sharp and broad resonances around the Larmor frequency and a resonance split by the electric quadrupole interaction. It was found that the appearance of the resonances is similar to the case of Si host (Izumikawa et al. Hyperfine Interact. 136/137:559–605, 2001). The quadrupole coupling constant for the split resonance was deduced as ∣eqQ/h∣ = 252(3) kHz under the assumption that it has <111> axial symmetry. And furthermore, assuming that the defect atom jumps thermally between the identical defect sites, the activation energy of the jump was deduced as 0.4 ± 0.1 eV. 相似文献
27.
Serine‐Selective Aerobic Cleavage of Peptides and a Protein Using a Water‐Soluble Copper–Organoradical Conjugate 下载免费PDF全文
Yohei Seki Dr. Kana Tanabe Dr. Daisuke Sasaki Dr. Youhei Sohma Dr. Kounosuke Oisaki Prof. Dr. Motomu Kanai 《Angewandte Chemie (International ed. in English)》2014,53(25):6501-6505
The site‐specific cleavage of peptide bonds is an important chemical modification of biologically relevant macromolecules. The reaction is not only used for routine structural determination of peptides, but is also a potential artificial modulator of protein function. Realizing the substrate scope beyond the conventional chemical or enzymatic cleavage of peptide bonds is, however, a formidable challenge. Here we report a serine‐selective peptide‐cleavage protocol that proceeds at room temperature and near neutral pH value, through mild aerobic oxidation promoted by a water‐soluble copper–organoradical conjugate. The method is applicable to the site‐selective cleavage of polypeptides that possess various functional groups. Peptides comprising D ‐amino acids or sensitive disulfide pairs are competent substrates. The system is extendable to the site‐selective cleavage of a native protein, ubiquitin, which comprises more than 70 amino acid residues. 相似文献
28.
In this Review, we summarize the current state of the art in late‐transition‐metal‐catalyzed reactions of acyl fluorides, covering both their synthesis and further transformations. In organic reactions, the relationship between stability and reactivity of the starting substrates is usually characterized by a trade‐off. Yet, acyl fluorides display a very good balance between these properties, which is mostly due to their moderate electrophilicity. Thus, acyl fluorides (RCOF) can be used as versatile building blocks in transition‐metal‐catalyzed reactions, for example, as an “RCO” source in acyl coupling reactions, as an “R” source in decarbonylative coupling reactions, and as an “F” source in fluorination reactions. Starting from the cleavage of the acyl C?F bond in acyl fluorides, various transformations are accessible, including C?C, C?H, C?B, and C?F bond‐forming reactions that are catalyzed by transition‐metal catalysts that contain the Group 9–11 metals Co, Rh, Ir, Ni, Pd, or Cu. 相似文献
29.
30.
Tatsuro Ouchi Hidetake Miyazaki Hidetoshi Arimura Fumitaka Tasaka Atsushi Hamada Yuichi Ohya 《Journal of polymer science. Part A, Polymer chemistry》2002,40(10):1426-1432
Amphiphilic AB‐type diblock copolymers composed of hydrophobic poly(L ‐lactide) (PLA) segments and hydrophilic poly(glycolic acid lysine) [poly(Glc‐Lys)] segments with amino side‐chain groups self‐associated to form PLA‐based polymeric micelles with amino surfaces in an aqueous solution. The average diameter of the loose core–shell polymeric micelles for poly(Glc‐Lys) [number‐average molecular weight (Mn) = 1240]‐b‐PLA (Mn = 7000) obtained by a dimethyl sulfoxide/water dialysis method was estimated to be about 50 nm in water by dynamic light scattering measurements. The size and shape of the obtained polymeric micelles were further observed with transmission electron microscopy and atomic force microscopy. To investigate the possibility of applying the obtained PLA‐based polymeric micelles as bioabsorbable vehicles for hydrophobic drugs, we tested the entrapment of drugs in poly(Glc‐Lys) (Mn = 1240)‐b‐PLA (Mn = 7000) micelles and their release with doxorubicin as a hydrophobic drug. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1426–1432, 2002 相似文献