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71.
72.
A novel bis(beta-cyclodextrin) was synthesized, and its binding behavior with steroids was investigated to demonstrate that the cooperative co-inclusion of guest and tether by two cyclodextrin moieties is operative to afford the highest molecular selectivity of up to 3.6 for deoxycholate over taurocholate. 相似文献
73.
The stereocontrolled synthesis of oligodeoxyribonucleoside phosphorothioates (PS-ODNs) using nucleoside 3'-O-oxazaphospholidine derivatives as monomer units is described. 2-Chloro-1,3,2-oxazaphospholidine derivatives were prepared from six kinds of enantiopure 1,2-amino alcohols and used for the phosphitylation reactions of 5'-O-protected nucleosides. A detailed study of these reactions revealed that the diastereoselectivity of the reaction depended on the structure of the enantiopure 1,2-amino alcohol, the reaction temperature, and the amine used as a scavenger of HCl. In addition, ab initio molecular orbital calculations for the 2-chlorooxazaphospholidine derivatives were carried out to elucidate the mechanism of these diastereoselective phosphitylation reactions. The LUMO of the 2-chloro-5-phenyloxazaphospholidine derivatives on the phosphorus atom was found to be almost orthogonal to the P-Cl bond. This LUMO may be involved in the phosphitylation reactions with predominant retention of the P-configuration. A series of dialkyl(cyanomethyl)ammonium salts were developed and used as activators for the condensation reactions of the diastereopure nucleoside 3'-O-oxazaphospholidines with 3'-O-protected nucleosides. In the presence of the new activators, the reactions proceeded rapidly to give the corresponding dinucleoside phosphite triesters. The diastereoselectivity of the condensation reaction did not depend on the counteranion but on the structure of the dialkyl(cyanomethyl)amine. In the presence of the activator, which consists of a relatively small dialkyl(cyanomethyl)amine, the condensation proceeded with excellent diastereoselectivity. After sulfurization and deprotection, diastereopure (R(p))- and (S(p))-dinucleoside phosphorothioates were obtained in excellent yields. The present methodology was also applied to the solid-phase synthesis of stereoregulated PS-ODNs. all-(R(p))-[T(PS)](3)T, all-(S(p))-[T(PS)](3)T, all-(R(p))-d[G(PS)A(PS)C(PS)]T, and all-(R(p))-[T(PS)](9)T were synthesized on a highly cross-linked polystyrene resin. 相似文献
74.
When milled together with bismuth shot in the presence of allyl halide, aromatic aldehydes readily underwent a Barbier-type allylation to afford the corresponding homoallyl alcohols in good yield. In contrast to the failure in solution reaction, aromatic ketones also underwent allylic carbonyl addition under solvent-free conditions to give the expected tertiary homoallyl alcohols in moderate to good yield. 相似文献
75.
Five Ci-Se...O...Se-Ci atoms in anthraquinone and 9-(methoxy)anthracene bearing phenylselanyl groups at 1,8-positions align linearly, the origin of which is shown to be a nonbonded 5c-6e interaction of the five atoms. 相似文献
76.
Masaharu Ueno Satoshi D. Ohmura Makoto Wada Norikazu Miyoshi 《Tetrahedron letters》2019,60(7):570-573
We developed an environmentally friendly method for aerobic oxidation of alcohols using a commercially available, relatively benign bismuth salt as a catalyst. We found that the catalytic combination of BiBr3 with nitric acid is key for enhancing the reactivity. The reaction proceeds well under air, making the use of pure oxygen unnecessary. Each of the primary or secondary alcohols tested was oxidized to the corresponding aldehydes or ketones using this protocol. 相似文献
77.
Kondo T Kaneko Y Taguchi Y Nakamura A Okada T Shiotsuki M Ura Y Wada K Mitsudo TA 《Journal of the American Chemical Society》2002,124(24):6824-6825
Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions. 相似文献
78.
We revealed that in ATX-S10.Na(II)(13,17-bis (1-carboxypropionyl) carbamoylethyl-8-etheny-2-hydroxy-3-hydroxyiminoethylidene-2,7,12,18-tetraethyl porphyrin sodium)-mediated photodynamic therapy using 667 nm nanosecond-pulsed light excitation at a peak intensity of 2.0 MW/cm(2), phototoxicity increased with decreasing pulse repetition rate in the range of 5-30 Hz for A549 cell cultures. To examine the relation between the reaction mechanism and measured phototoxicity, we carefully measured the kinetics of photochemical oxygen consumption and photobleaching during irradiation of ATX-S10.Na(II)-sensitized A549 monolayer cultures. Measurements of oxygen consumption with a microelectrode, which was performed just above the cells, showed that there was no significant difference between the magnitudes of decrease in oxygen at the three repetition rates at the same cumulative fluence. Loss of ATX-S10.Na(II) fluorescence intensity also exhibited little repetition rate dependence when compared at the same cumulative fluence. We investigated the correlation between oxygen consumption and photobleaching during irradiation and obtained "fluorescence-oxygen diagrams." The diagrams showed dynamic changes between oxygen-dependent and oxygen-independent photobleaching at the higher repetition rates of 10 and 30 Hz, whereas such change was not clearly seen over the whole irradiation time at 5 Hz. These results suggest that the reduced phototoxicity at high repetition rates might be due to an oxygen-independent reaction. We presumed that the change in the reaction mechanism was associated with the local concentrations of the photosensitizer and oxygen in cells during irradiation. 相似文献
79.
Nishiyama Y Kaneda M Saito R Mori T Wada T Inoue Y 《Journal of the American Chemical Society》2004,126(21):6568-6569
In the enantiodifferentiating photoaddition of ROH (R = Me, Et, i-Pr) to 1,1-diphenylpropene sensitized by fructosyl 1,4-naphthalenedicarboxylate in supercritical carbon dioxide, the enantiomeric excess of photoadduct increased with increasing bulkiness of the alcohol at all pressures used, with an accompanying sudden jump at the critical density, for which the enhanced clustering of alcohol, particularly in the subcritical pressure region, was revealed to be responsible from the fluorescence spectral examinations. 相似文献
80.
Warô Nakanishi Satoko Hayashi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1833-1837
The lone pair-lone pair repulsion plays an important role in the nonbonded P;;;P interaction in naphthalene 1,8-positions. The conformations around P and Se in 8-(PhSe)-1-(Ph 2 P=O)C 10 H 6 are determined by the attractive O;;;Se--C 3c-4e type interaction. The P;;;Se interaction in the 1,8-positions is also discussed. 相似文献