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141.
Nine 1-[2-(1-substituted)ethyl-3-benzothienyl]-2-(2-methyl-3-benzothienyl)hexafluorocyclopentenes (4-substituted benzoyloxy, N-arylcarbamoyloxy, and aryloxycarbonyloxy) were synthesized. They showed diastereoselective photochromic ring closure upon UV irradiation. Among them, 4-nitrophenoxycarbonyloxy-substituted compound recorded a remarkable 94% diastereomer excess with 91% conversion to the closed form. 相似文献
142.
Previously, O-selective phosphorylation on polymer supports in the N-unprotected phosphoramidite method could not be carried out because the amino groups of dA and dC have high reactivity toward tervalent phosphorus(III)-type phosphitylating reagents. In this paper, we developed a new coupling strategy named the "activated phosphite method" in which the phosphitylation is mediated by phosphite triester intermediates 1. Application of 1-hydroxybenzotriazole as the promoter to the solid-phase synthesis resulted in excellent O-selectivity of more than 99.7%. This O-selectivity was explained by the frontier molecular orbital interactions between the reactive intermediates and the nucleophiles such as the amino or hydroxyl groups of nucleosides. Furthermore, longer oligonucleotides were synthesized not only by a manual operation but also by a DNA synthesizer. The utility of our new method was demonstrated by the successful synthesis of a base-labile modified oligodeoxyribonucleotide having 4-N-acetyldeoxycytidine residues. Finally, DNA 20-mers containing dA or dC could be synthesized in good yields by use of a combined reagent of 6-trifluoromethyl-1-hydroxybenzotriazole and benzimidazolium triflate. 相似文献
143.
Takeishi S Rant U Fujiwara T Buchholz K Usuki T Arinaga K Takemoto K Yamaguchi Y Tornow M Fujita S Abstreiter G Yokoyama N 《The Journal of chemical physics》2004,120(12):5501-5504
DNA oligo-nucleotides, localized at Au metal electrodes in aqueous solution, are found to be released when applying a negative bias voltage to the electrode. The release was confirmed by monitoring the intensity of the fluorescence of cyanine dyes (Cy3) linked to the 5' end of the DNA. The threshold voltage of the release changes depending on the kind of linker added to the DNA 3'-terminal. The amount of released DNA depends on the duration of the voltage pulse. Using this technique, we can retain DNA at Au electrodes or Au needles, and release the desired amount of DNA at a precise location in a target. The results suggest that DNA injection into living cells is possible with this method. 相似文献
144.
Hashimoto A Przybyl AK Linders JT Kodato S Tian X Deschamps JR George C Flippen-Anderson JL Jacobson AE Rice KC 《The Journal of organic chemistry》2004,69(16):5322-5327
The synthesis of the ortho- and para-e isomers in the oxide-bridged 5-phenylmorphan series of rigid tetracyclic compounds was accomplished via rac-5-(2-fluoro-5-nitrophenyl)-2-methyl-2-azabicyclo[3.3.1]nonan-9beta-ol ((+/-)-10), an intermediate containing an aromatic nitro-activated fluorine atom. The fluorine atom was used as the leaving group for the formation of the strained tetracyclic trans-fused 5,6-ring system in rac-(1alpha,4aalpha,9aalpha)-1,3,4,9a-tetrahydro-2-methyl-6-nitro-2H-1,4a-propanobenzofuro[2,3-c]pyridine ((+/-)-11), although preference for cis ring fusion during the formation of tricyclic tetra- and hexahydrodibenzofurans has been well-documented. Single-crystal X-ray crystallographic study of the desired para-e isomer ((+/-)-2), as well as of two intermediates in its synthesis, provided assurance of the correct structures. The e-isomers are among the last of the 12 oxide-bridged 5-phenylmorphans to be synthesized. We envisioned the syntheses of these rigid, tetracyclic compounds in order to determine the three-dimensional pattern of a ligand that would enable interaction with opioid receptors as agonists or antagonists. 相似文献
145.
Kondoh H Iwasaki M Shimada T Amemiya K Yokoyama T Ohta T Shimomura M Kono S 《Physical review letters》2003,90(6):066102
The adsorption structure of methylthiolate (CH3S) adsorbed on Au(111), a long-standing controversial issue, has been unambiguously determined by scanned-energy and scanned-angle S 2p photoelectron diffraction. The methylthiolate molecules are found to occupy atop sites with a S-Au distance of 2.42 +/- 0.03 A. The angular distribution of the S 2p photoelectrons due to forward scattering reveals that the S-C bond is inclined by approximately 50 degrees from the surface normal towards both the [211] and [121] (nearest-neighbor thiolate) directions. 相似文献
146.
Ultraviolet second-harmonic generation in first-order periodically poled MgO:LiNbO3 is presented. Using a high-voltage multipulse application method, we fabricated a first-order nonlinear grating with a period of 1.8 microm and depth of approximately 150 microm over 10-mm interaction length in a 1-mm-thick MgO:LiNbO3 substrate. In a single-pass configuration, continuous-wave 30-mW UV light at 362.5 nm was generated for a fundamental power of 522 mW, corresponding to a normalized conversion efficiency of 11%/W. 相似文献
147.
Jones DJ Holman KW Notcutt M Ye J Chandalia J Jiang LA Ippen EP Yokoyama H 《Optics letters》2003,28(10):813-815
Using high-bandwidth feedback, we have synchronized the pulse train from a mode-locked semiconductor laser to an external optical atomic clock signal and achieved what is to our knowledge the lowest timing jitter to date (22 fs, integrated from 1 Hz to 100 MHz) for such devices. The performance is limited by the intrinsic noise of the phase detector used for timing-jitter measurement. We expect such a highly stable device to play an important role in fiber-network-based precise time/frequency distribution. 相似文献
148.
Nomoto A Mitsuoka H Ozeki H Kobuke Y 《Chemical communications (Cambridge, England)》2003,(9):1074-1075
Introducing a porphyrin bearing electron acceptor onto a self-assembled monolayer (SAM) using a supramolecular method to form a hetero-dimer increased the photocurrent value compared with using porphyrin without an electron acceptor. 相似文献
149.
Yokoyama Y Shiraishi H Tani Y Yokoyama Y Yamaguchi Y 《Journal of the American Chemical Society》2003,125(24):7194-7195
Introduction of an asymmetric center to C-2 of one of the benzothiophene rings of bisbenzothienylperfluorocyclopentene results in a highly diastereoselective photochromic system. The stereogenic center bears a hydrogen atom, a methyl group, and a methoxymethoxy group. The steric as well as the electronic repulsions gave an 87-88% diastereomer excess in various solvents at room temperature with 80-85% conversion to the colored form. The enantioselective synthesis was also carried out. Upon photoirradiation in hexane, a change in optical rotation at 820 nm, where neither the open form nor the colored form absorbs light, was observed repeatedly. 相似文献
150.
Kanai M Yasumoto M Kuriyama Y Inomiya K Katsuhara Y Higashiyama K Ishii A 《Organic letters》2003,5(7):1007-1010
[reaction: see text] The highly regioselective hydrogenolysis of bis(alpha-methylbenzyl)amine derivatives proceeded with influence not from the electronic effect but from the steric effect of the trifluoromethyl substituent on the aromatic ring to provide a practical asymmetric synthesis of trifluoromethyl-substituted alpha-phenylethylamines. 相似文献