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71.
Concise construction of the trans-fused 7/7/6/6 tetracyclic ether part of hemibrevetoxin B (1) was achieved by a convergent strategy based on coupling reaction of an acyl anion equivalent, reductive cyclization of an α,ε-dihydroxyketone, and introduction of a methyl group at the central ring junction by the Nicolaou method. The resultant tetracyclic ether was transformed into the known intermediate, which was already converted to 1 by the Yamamoto group, thereby completing the formal total synthesis of 1. 相似文献
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Pumping dye-doped organic polymer by interference pattern of a frequency-doubled Nd:YAG 532 nm laser to induce a periodic gain-structure and confining it within a stable optical resonator, the oscillation output can be effectively enhanced in comparison with either that of uniform irradiation, i.e., pumping, or of distributed feedback (DFB) operation, and the oscillation wavelength becomes tunable by adjusting the period of the interference pattern. Using Rhodamine-B as a dopant over the range from 200 to 1000 ppm, the oscillation output was enhanced by - 10 dB, which was larger than the output of the uniform irradiation and was - 30% greater than the DFB scheme. Moreover, changing the period of the interference pattern by adjusting the setting angle of the Koster prism enables us to vary the oscillation wavelength around 600 nm. 相似文献
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Kenshu Fujiwara Yuta Hirose Hidetoshi Kawai Takanori Suzuki 《Tetrahedron letters》2010,51(32):4263-4546
Armatol F, isolated from the red alga Chondria armata as a polyether triterpene, has a solitary oxepane (A-ring) and a fused tricyclic ether moiety (BCD-ring). The A-ring features a rare cis-relationship between the hydroxy group at the quaternary carbon C6 and the carbon chain at C7. As part of our program toward the total synthesis of armatol F, a new stereoselective method for the construction of the C6 and C7 stereocenters has been developed based on chirality-transferring Ireland-Claisen rearrangement. The A-ring skeleton has also been synthesized from the rearrangement product by a process including ring-closing olefin metathesis. 相似文献
78.
Kaori Kobayashi Takanori Matsui Shozo Tsunekawa 《Journal of Molecular Spectroscopy》2011,269(2):242-247
The trans-ethyl methyl ether molecule has three low-lying torsional modes, that is, two inequivalent methyl internal rotations and an asymmetric skeletal torsion. The internal rotations of the CCH3 and OCH3 methyl rotors and the skeletal torsion correspond to the vibrational modes, ν28, ν29 and ν30 respectively. In this study, the microwave absorption spectrum in the ν28 = 1 CCH3 torsional state was analyzed for the first time. Nine hundred fifty seven lines up to J = 48 and K = 4 were assigned, and the rotational, centrifugal distortion and internal rotational tunneling parameters were determined with the use of a tunneling matrix formalism. By combining the present results on the ν28 = 1 torsional state with those for the ν30 = 1 skeletal torsional state and the ν29 = 1 OCH3 torsional state, torsional couplings are estimated in order to understand quantitatively the inverted A/E sequence patterns observed for those three excited torsional states. 相似文献
79.
Masahiro Hakariya Yoshinori Arisaka Hiroki Masuda Tetsuya Yoda Takanori Iwata Nobuhiko Yui 《Macromolecular bioscience》2023,23(2):2200438
Cancer cells recognize physical cues transmitted from the surrounding microenvironment, and accordingly alter the migration and chemosensitivity. Cell adhesive biomaterials with tunable physical properties can contribute to the understanding of cancer cell responses, and development of new cancer therapies. Previously, it was reported that polyrotaxane-based surfaces with molecular mobility effectively modulate cellular functions via the yes-associated protein (YAP)-related signaling pathway. In the present study, the impact of molecular mobility of polyrotaxane surfaces on the migration and chemosensitivity of lung (A549), pancreatic (BxPC-3), and breast cancer (MDA-MB-231) cell lines is investigated, and it is found that the cellular spreading of adherent A549 and BxPC-3 cells and nuclear YAP translocation are promoted on low-mobility surfaces, suggesting that cancer cells alter their subcellular YAP localization in response to molecular mobility. Furthermore, low-mobility surfaces suppress cellular migration more than high-mobility surfaces. Additionally, low-mobility surfaces promote the cisplatin chemosensitivity of each cancer cell line to a greater extent than high-mobility surfaces. These results suggest that the molecular mobility of polyrotaxane surfaces suppresses cellular migration and enhances chemosensitivity via the subcellular translocation of YAP in cancer cells. Biointerfaces based on polyrotaxanes can thus be a new platform for elucidating cancer cell migration and chemoresistance mechanisms. 相似文献
80.
Takanori Shibata Tsubasa Shizuno 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(21):5514-5517
The first catalytic and enantioselective C H alkylation of ferrocene derivatives with various alkenes was achieved. A cationic iridium complex, having a chiral diene ligand, and an isoquinolyl moiety as a directing group are essential for regioselective and enantioselective C H bond activation. 相似文献