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Stereodivergent Synthesis and Stereochemical Reassignment of the C79–C104 Fragment of Symbiodinolide
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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
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Manabu KuroboshiTomotake Yano Shogo KamenoueHiromu Kawakubo Hideo Tanaka 《Tetrahedron》2011,67(32):5825-5831
Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al3+, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields. 相似文献
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W.M. Shu Y. Kawakubo M.F. Nishi 《Applied Physics A: Materials Science & Processing》2003,76(3):421-425
Recovery of tritium from co-deposited layers formed in deuterium–tritium plasma operations of the TFTR (Tokamak Fusion Test
Reactor) was investigated by the use of an ArF excimer laser operating at the wavelength of 193 nm. At the laser energy density
of 0.1 J/cm2, a transient spike of the tritium-release rate was observed at initial irradiation. Hydrogen isotopes were released in the
form of hydrogen-isotope molecules during the laser irradiation in vacuum, suggesting that tritium can be recovered readily
from the released gases. In a second experiment, hydrogen (tritium) recovery from the co-deposited layers on JT-60 tiles that
had experienced hydrogen-plasma operations was investigated by laser ablation with a focused beam of the excimer laser. The
removal rate of the co-deposited layers was quite low when the laser energy density was smaller than the ablation threshold
(1.0 J/cm2), but reached 1.1 μm/pulse at the laser energy density of 7.6 J/cm2. The effective absorption coefficient in the co-deposited layers at the laser wavelength was determined to be 1.9 μm-1. The temperature of the surface during the irradiation at the laser energy density of 0.5 J/cm2 was measured on the basis of Planck’s law of radiation, and the maximum temperature during the irradiation decreased from
3570 K at the initial irradiation to 2550 K at the 1000th pulse of the irradiation.
Received: 5 August 2002 / Accepted: 7 August 2002 / Published online: 28 October 2002
RID="*"
ID="*"Corresponding author. Fax: +81-29/2825917, E-mail: shu@tpl.tokai.jaeri.go.jp 相似文献
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Motohashi S Nagase K Nakakita T Matsuo T Yoshida Y Kawakubo T Miura M Toriyama M Barybin MV 《The Journal of organic chemistry》2011,76(10):3922-3936
Enantiomerically pure (Z)-β-sulfinyl allylic alcohols of either handedness can be readily prepared from (Z)-β-sulfinyl enones using NaBH(4) or DIBAL reductants in the presence of LaCl(3) as a chelating agent. A chiral sulfoxide auxiliary induces the remote 1,2-asymmetric reduction (1,4-induction) to afford various chiral allylic alcohols in high yields with excellent stereoselectivities (up to 100% de). 相似文献
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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):1979-1983
Stereoselective and streamlined synthesis of the proposed C79–C104 fragment 2 of symbiodinolide ( 1 ), a polyol marine natural product with a molecular weight of 2860, was achieved. In the synthetic route, the proposed C79–C104 fragment 2 was synthesized by utilizing a Julia–Kocienski olefination and subsequent Sharpless asymmetric dihydroxylation as key transformations in a convergent manner. Detailed comparison of the 13C NMR chemical shifts between the natural product and the synthetic C79–C104 fragment 2 revealed that the stereostructure at the C91–C99 carbon chain moiety of symbiodinolide ( 1 ) should be reinvestigated. 相似文献
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Kazuyuki Torii Atsushi Kawakubo Dr. Xianjin Lin Prof. Dr. Tetsuaki Fujihara Prof. Dr. Tatsuo Yajima Prof. Dr. Yasushi Obora 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):4888-4892
A highly regioselective and stereoselective difunctionalization reaction of 1,3-diene with amine and disilane to form C−N and C−Si bonds via a one-step Pd/Cu/O2 system is disclosed. The difunctionalization reaction affords allylic silanes, including the allylic amine moiety, in up to 92 % yield in the absence of any acid, base, or external ligand. The developed synthetic methodology can be scaled to 100 g in high yield with high Z-selectivity, which demonstrates the feasibility of the reaction for industrial applications. 相似文献
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Yasutada Suzuki Terutomi Aruga Hiroyuki Kuwahara Miki Kitamura Tetsuo Kuwabara Susumu Kawakubo Masaaki Iwatsuki 《Analytical sciences》2004,20(6):975-977
A portable colorimeter using a red-green-blue light-emitting diode as a light source has been developed. An embedded controller sequentially turns emitters on and off, and acquires the signals detected by two photo diodes synchronized with their blinking. The controller calculates the absorbance and displays it on a liquid-crystal display. The whole system, including a 006P dry cell, is contained in a 100 x 70 x 50 mm aluminum case and its mass is 280 g. This colorimeter was successfully applied to the on-site determination of nitrite and iron in river-water. 相似文献
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Sasaki M Hayashi J Fujii M Koizumi K Fujita H Kobayashi M Kawakubo Y Ito A 《Journal of photochemistry and photobiology. B, Biology》2001,60(2-3):120-128
We propose a model of the intracellular delivery process in which fluorescein-labeled natural oligonucleotides (F-DNA) are transferred into the nuclei of cultured human keratinocytes. By encapsulation in neutral multilamellar lecithin liposomes, the F-DNA appeared to be protected against intracellular interactions with cellular materials and nuclease attacks in the cytoplasm during the process. The intracellular behavior of F-DNA and fluorescent phospholipid-labeled liposomes was observed by means of fluorescence analysis. Results showed that: F-DNA encapsulated in neutral multilamellar liposomes reached the cellular nuclei more efficiently than either free F-DNA, or F-DNA in unilamellar liposomes; the liposomal membranes appeared to be left in the cytoplasm. The reaction of F-DNA with complementary DNA was suggested by a rapid quenching of the fluorescence in the nucleus. In addition, the fluorescence decrease was evidently suppressed in the cytoplasm, indicating a protective effect of the neutral multilamellar liposomes against the interaction of F-DNA with cytoplasmic materials. The application of these findings to ‘photo’-antisense studies has been discussed, where suppression of a gene expression is attempted by using oligonucleotide-attached fluorescein with the aid of a photo-induced covalent binding property. 相似文献