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1.
Synthesis of Disaccharide Nucleosides by the O‐Glycosylation of Natural Nucleosides with Thioglycoside Donors 下载免费PDF全文
Prof. Shin Aoki Taketo Fukumoto Taiki Itoh Masayuki Kurihara Shigeto Saito Shin‐ya Komabiki 《化学:亚洲杂志》2015,10(3):740-751
Disaccharide nucleosides constitute an important group of naturally‐occurring sugar derivatives. In this study, we report on the synthesis of disaccharide nucleosides by the direct O‐glycosylation of nucleoside acceptors, such as adenosine, guanosine, thymidine, and cytidine, with glycosyl donors. Among the glycosyl donors tested, thioglycosides were found to give the corresponding disaccharide nucleosides in moderate to high chemical yields with the above nucleoside acceptors using p‐toluenesulfenyl chloride (TolSCl) and silver triflate (AgOTf) as promoters. The interaction of these promoters with nucleoside acceptors was examined by 1H NMR spectroscopic experiments. 相似文献
2.
Prof. Dr. Toshiyuki Itoh Dr. Shuichi Hayase Prof. Dr. Toshiki Nokami 《Chemical record (New York, N.Y.)》2023,23(9):e202300028
The incorporation of fluorine atoms into an organic compound can alter the chemical reactivity or biological activity of the resulting compound due to the strong electron withdrawing nature of the fluorine atom. We have synthesized many original gem-difluorinated compounds and described the results in four sections. The first section describes the synthesis of optically active-gem-difluorocyclopropanes via the chemo-enzymatic reaction; we applied these compounds to liquid crystalline molecules, then further discovered a potent DNA cleavage activity for the gem-difluorocyclopropane derivatives. The second section describes the synthesis of selectively gem-difluorinated compounds via a radical reaction; we synthesized fluorinated analogues of a sex pheromone of the male African sugarcane borer, Eldana saccharina, and used the compounds as proof for investigating the origin of pheromone molecule recognition on the receptor protein. The third involves the synthesis of 2,2-difluorinated-esters by visible light-driven radical addition of 2,2-difluoroacetate with alkenes or alkynes in the presence of an organic pigment. The last section describes the synthesis of gem-difluorinated compounds via the ring-opening of gem-difluorocyclopropanes. We further developed a novel method of synthesizing gem-difluorohomoallylic alcohols via the ring-opening of gem-difluorocyclopropane and aerobic oxidation by photo-irradiation in the presence of an organic pigment. Since gem-difluorinated compounds that were prepared by the present method have two olefinic moieties with a different reactivity at the terminal position, we accomplished the synthesis of four types of gem-difluorinated cyclic alkenols via the ring-closing-metathesis (RCM) reaction. 相似文献
3.
The demand for more efficient methods of establishing the undetermined stereochemistries of peptidic natural products continues unabated. A new method for microscale stereochemical determination was devised by integrating solid-phase synthesis, split-and-mix randomization, 18O/16O-encoding of d /l -configurations, tandem mass spectrometry, and biological evaluation. Here we applied gramicidin A as the molecule for a blind test. Gramicidin A and its 31 diastereomers were randomly prepared in microgram scale with 18O/16O-stereochemical encoding and subjected to MS/MS-structural determination and cytotoxicity assay. Only the parent gramicidin A was selected from among the 32 stereoisomers, validating the high reliability of the present strategy. 相似文献
4.
A free-piston shock tunnel (FPST) is one of the most useful ground testing facilities for hypervelocity flow research of re-entry vehicles and scramjet engines. For an efficient operation with tuned piston motion, the design of facility and the comprehension of the physical phenomena in a FPST, a numerical simulation which can properly predicts the flow with actual losses is required. But there are few successful numerical methods which can simulate its overall performance. In the present study, numerical method was developed by using the KRC shock capturing scheme and by modeling the flow losses in suitable forms for a quasi-1D numerical computation. The present numerical results were compared with the data obtained in two different facilities, T4 and T5. The applicability of the present numerical method as a design tool is discussed briefly.This article was processed using Springer-Verlag TEX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society. 相似文献
5.
This paper describes the verification of the accuracy of residual stress measurement by the hole-drilling method. The strain measurement is simulated by the use of the indirect fictitious-boundary integral method. As an example, a finite rectangular plate subjected to initial stress is treated, and a simulated measurement of the residual stress is made using the strain relieved during hole drilling. The accuracy of residual stress measurement is estimated by comparing the simulated measured residual stress with the actual residual stress, i.e., the given initial stress. The results are shown for various distances and angles of strain gages. Also, the influences of the eccentricity of the hole from the center of the strain gages and the effect of a boundary near the hole are examined. 相似文献
6.
7.
Herein we report the production of enantiopure epoxides through biocatalysis using recombinant Escherichia coli cells expressing Rhodococcus sp. ST-10 styrene monooxygenase (SMO) and Leifsonia sp. S749 alcohol dehydrogenase (LSADH) genes are described. Rhodococcus sp. ST-10 SMO catalyzed the epoxidation of various alkenes, including styrene derivatives, vinyl pyridines, and linear alkenes, to give (S)-epoxides. NADH was regenerated by the reduction of NAD+ by LSADH with 2-propanol. The E. coli biocatalyst was used in an aqueous/organic biphasic reaction system and the reaction conditions were optimized. Under the optimized conditions, 170 mM of (S)-styrene oxide was obtained from styrene in the organic phase with excellent enantiomeric excess (99.8%). This biocatalytic process was used to synthesize various (S)-epoxides. 相似文献
8.
Abstract Color centers in rutile-structured MgF2 single crystals irradiated at 20K/360K by reactor neutrons are investigated spectroscopically at LNT. Four different types of the F-F vacancy bond in MgF2 are possibly identified to the observed absorption bands as due to the F2 centers; instead of previous assignments, the 300nm band to the F2(D2h), the 325nm band to the F2(C1), the 355nm band to the F2(C2v), and the 400nm band to the F2(C2h) centers. 相似文献
9.
Kazuhiro Marumo Manabu Itoh Sungmin Kang Koichi Sakajiri Junji Watanabe 《Liquid crystals》2013,40(2):234-238
Galactose derivatives were explored as chiral dopants, effective for inducing chiral nematic liquid crystal (LC) phases. Galactose bearing O-isopropylidene substituents at the C3 and C4 and butoxybiphenyl substituents at the C2 and C6 positions exhibits a high helical twisting power (HTP) value of ?74.4 μm?1. Such a high HTP value for the galactose derivative is attributed to (1) linkage of the C3 and C4 carbons with the O-isopropylidene substituent, which places the C2 and C6 substitutes in a skew arrangement at a large angle and (2) enhancement of the affinity with the host nematic LCs by incorporating aromatic substituents at the C2 and C6 positions that are similar to those in the host. 相似文献
10.
Dual Chemical Modification of a Polytheonamide Mimic: Rational Design and Synthesis of Ion‐Channel‐Forming 48‐mer Peptides with Potent Cytotoxicity 下载免费PDF全文
Atsushi Hayata Dr. Hiroaki Itoh Shoko Matsutaka Prof.Dr. Masayuki Inoue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3370-3377
Polytheonamide B ( 1 ) is a natural peptide that displays potent cytotoxicity against P388 mouse leukemia cells (IC50=0.098 nm ). Linear 48‐mer 1 is known to form monovalent cation channels on binding to lipid bilayers. We previously developed a fully synthetic route to 1 , and then achieved the design and synthesis of a structurally simplified analogue of 1 , namely, dansylated polytheonamide mimic 2 . Although the synthetically more accessible 2 was found to emulate the channel function of 1 , its cytotoxicity was decreased 120‐fold. Herein, the chemical preparation and biological evaluation of seven analogues 3 – 9 of 2 are reported. Compounds 3 – 9 were modified at their N terminus and/or the side chain of residue 44 of 2 to alter their physicochemical properties. The total synthesis of 3 – 9 was accomplished in a unified fashion by a combination of solid‐phase and solution‐phase chemistry. Systematic evaluation of the hydrophobicities, single‐channel currents, ion‐exchange activities, and cytotoxicities of 3 – 9 revealed that their hydrophobicities are correlated with the total magnitude of ion exchange and determine their cytotoxic potency. Consequently, the most hydrophobic analogue 9 exhibited the lowest IC50 value, which is comparable to that of 1 . Therefore, these results clarified that the bioactivity of the polytheonamide‐based peptides can be rationally controlled by changing their hydrophobicity at the N and C termini of the 48‐amino‐acid sequence. 相似文献