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31.
By the self-immolative asymmetric synthesis, optically pure key intermediate β-piperonyl-γ-lactone (R)-(+)- was found to be prepared in reasonable yield from the easily available chiral γ-lactone synthon () which had been also reported to give an antipode (S)-(-)-. The optically pure (R)-(+)- was shown to be converted successfully into several optically pure natural lignan lactones. 相似文献
32.
Hoteling AJ Kawaoka K Goodberlet MC Yu WM Owens KG 《Rapid communications in mass spectrometry : RCM》2003,17(14):1671-1676
Details of the optimization of the collision-induced dissociation (CID) process, using a collision cell on a matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometer, are described using poly(ethylene glycol) 1000 (PEG 1000) as a model analyte. The effects of collision gas identity (helium, air, and argon), as well as collision gas pressure, on the resulting MS/MS data were investigated. With PEG 1000, helium was found to give the best results with respect to signal-to-noise (S/N) ratio. The optimum pressure for each gas was found to be in the range where the precursor ion signal was attenuated to approximately 30-50% for helium and 40-60% for argon. The effect of cation choice (Li, Na, and K) on the CID of PEG was also studied. CID spectra were produced for each, but PEG cationized with lithium was found to produce the spectra with the highest S/N ratio. The MALDI-TOF CID spectra that were generated for PEG were compared with the high-energy and low-energy MS/MS spectra obtained from a sector mass spectrometer and from a triple quadrupole mass spectrometer, respectively. The results observed for PEG confirm that CID on a MALDI-TOF mass spectrometer is a high-energy MS/MS technique. 相似文献
33.
(+)-Steganacin was synthesized in a new and highly specific asymmetric pathway based on the novel application of chiral γ-lactone as a chiral synthon. By this synthesis the absolute stereochemistry of natural (?)-steganacin could be determined in unequivocal way. 相似文献
34.
Yoshinori Kadoma Takashi Toida Kenji Takeda Keikichi Uno Yoshio Iwakura 《Journal of polymer science. Part A, Polymer chemistry》1975,13(3):707-716
The polymerization of picryl (PMA), 2,4-dinitrophenyl (2,4-DNMA),2,6-dinitrophenyl (2,6-DNMA), 2-methyl-4,6-dinitrophenyl (MDNMA), and 2,6-dimethylphenyl methacrylates (DMMA) was carried out in benzene at 60°C. PMA, 2,6-DNMA, and MDNMA did not undergo radical homopolymerization, while 2,4-DNMA and DMMA did. The results suggest that the growing radical readily attacks the oxygen atom of the nitro group at the 2 position of the terminal phenyl group due to the steric effect of the substituent at the 6 position, resulting in chain termination. PMA formed a charge-transfer complex with 2-naphthyl methacrylate (NMA). The stoichiometric composition of this complex was shown to be 1:1 molar complex. PMA was readily copolymerized with NMA. The amount of solvent affected the composition of the copolymer obtained at a given same mole fraction in feed. The results suggest that charge-transfer interaction between the ester groups affects the copolymerization mechanism. 相似文献
35.
Introduction of atropisomeric axes into a bent bispyridine ligand leads to the quantitative formation of a complex mixture of atropisomeric M2L4 cages upon treatment with metal ions. Whereas the isomer ratio of the obtained cage mixture, consisting of up to 42 isomers, is insensitive to temperature and solvent, the quantitative convergence from the mixture to a single isomer is accomplished upon encapsulation of a large spherical guest, namely fullerene C60. The observed isomerization with other guests depends largely on their size and shape (e.g., <10 and 82% convergence with planar triphenylene and bowl-shaped corannulene guests, respectively). Besides the unusual guest-induced convergence, the present cage mixture displays the strongest guest emission (ΦF = 68%) among previously reported MnLm cages and capsules, upon encapsulation of a BODIPY dye in water.A complex mixture of atropisomeric M2L4 cages is shown to undergo perfect convergence to a single isomer upon encapsulation of spherical C60 in water. Moreover, the cage mixture displays very strong guest emission upon encapsulation of a BODIPY dye. 相似文献
36.
Hiroshi Maruoka Kenji Yamagata Fumi Okabe Yukihiko Tomioka 《Journal of heterocyclic chemistry》2005,42(4):717-721
A series of cyclic sulfonium ylides 4a‐h reacted with titanium( IV ) chloride in the presence of triethyl‐amine to give the corresponding fused 2,3‐dihydro‐1H‐thieno[3,4‐b]pyrroles 5a‐h , via a ring opening and recyclization. In contrast, treatment of compounds 4a, 4b, 4e and 4f with titanium(IV) chloride, triethy‐lamine and dimethylamine hydrochloride gave the corresponding thiophenes 6a, 6b, 6e and 6f . Furthermore, compounds 6a and 6b easily underwent cyclization with sodium hydride to afford the corresponding 5a and 5b . 相似文献
37.
Geometry optimizations at the UHF/6-31G* and UMP2/6-31G* levels of theory were performed to find the transition state in the interconversion between norbornadiene (N) and quadricyclane (Q) radical cations. Two transition structures, TS+·1 and TS+·2, were obtained which have C1 and C2 symmetry, respectively. Vibrational analysis at the UHF and UMP2 levels of theory and IRC calculation showed that TS+·1 is the true transition state connecting N+· and Q+·, while TS+·2 is a second order saddle point. 相似文献
38.
Sano S Takehisa T Ogawa S Yokoyama K Nagao Y 《Chemical & pharmaceutical bulletin》2002,50(9):1300-1302
Tetrasubstituted (Z)-alkenes were readily prepared through the Horner-Wadsworth-Emmons reactions of methyl 2-[bis(2,2,2-trifluoroethyl)phosphono]propionate with aryl alkyl ketones by employing Sn(OSO(2)CF(3))(2) and N-ethylpiperidine. 相似文献
39.
Yagi Kiyohito Hamada Kenji Hlrata Kazumasa Miyamoto Kazuihisa Miura Yoshiharu Akano Tohru Fukatu Kiyomi Ikuta Yoshiaki Nakamura Hiroshi K. 《Applied biochemistry and biotechnology》1994,(1):225-232
A marine green alga,Chlamydomonas sp. strain MGA161 was cultivated under illumination of red and white lights. The growth rate under red light illumination
was almost the same as that in the basic conditions under white light illumination, but red light-grown cells accumulated
almost twice as much starch as white light-grown cells. Although there was a slight decrease in carbonic anhydrase activity,
red light-illuminated cells had almost 2.3 times the fructose-l,6-diphos-phatase activity of white light-illuminated cells.
Red light might stimulate starch accumulation by increasing the amounts of enzymes related to carbon fixation through the
phytochrome system. Cells grown under red light degraded 1.6 times as much starch and produced 1.7 times as much hydrogen
and 1.6 times as much ethanol compared with cells grown under white light during 12 h of dark anaerobic fermentation. 相似文献
40.
(-)-Pestalotin [(6S, l'S)-6-(1'-hydroxypentyl)-4-methoxy-5,6-d dihydro-2-pyrone 1a]and its three other stereoisomers were synthesized either by utilizing the Sharpless asymmetric epoxidation as the keystep or by derivation from D-(+)-glyceraldehyde acetonide. 相似文献