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161.
[structure: see text] The complete stereostructure of the natural product (+)-glisoprenin A had been predicted via a novel application of chiral lanthanide shift reagents. Confirmation of the predicted stereostructure of (+)-glisoprenin A and validation of the chiral lanthanide shift approach have now been achieved through total synthesis. 相似文献
162.
163.
17β-Hydroxy-5α-androstan-2α,3α-anti(R)-episulfoxide on treatment with methanol and ethanol in the presence of a trace amount of sulfuric acid gave diastereomers of bis((2β-methoxy- and 2β-ethoxy-17β-hydroxy-5α-androstan-3α-yl) disulfide S-monoxides respectively. The absolute configuration of the compounds was established by their Grignard reactions leading to diastereomeric phenyl sulfoxides stereoaspecifically. 相似文献
164.
Y. Masada K. Hashimoto T. Inoue Y. Sumida T. Kishi Y. Suwa 《Journal of separation science》1979,2(7):400-404
A novel method is described for the preparation of stable glass capillary columns (glass open tubular columns), including the etching and formation of a polymer film on the inner glass capillary surfaces. The approach used here is based on low-temperature plasma etching and polymerization. Under the influence of a field of radio frequency discharge, low pressure gases of fluoric compounds, introduced into the glass capillary tube, generate excited fluorine radicals which etch the inner surface. The plasma of organosilicone monomer in the glass capillary yields a uniform polymerized film on the inner surface. The resultant material functions as a good stationary phase for glass capillary gas chromatography (GC2). The inner surfaces treated with such a plasma, can be studied by means of a scanning electron microscope (SEM). The flexibility of this method permits the use of various stationary phases and surface modification. 相似文献
165.
The bioluminescence of the American firefly Photinus is due to the reaction of 2-(6-hydroxybenzothiazol-2-yl)-Δ2-1,3-thiazoline-4-carboxylic acid (“firefly luciferin”) with the enzyme luciferase in the presence of ATP and magnesium ion. In the crustacean Cypridina, on the other hand, the bioluminescence is due to the reaction of a luciferase with 8-(3-guanidinopropyl)-6-indol-3-yl-2-(1-methylpropyl)-3,7-dihydroimidazo[1,2-a]-pyrazin-3-one (“Cypridina luciferin”). The luciferin in Latia is 1,3,3-trimethyl-2-(4-formyloxy-3-methyl-3-butenyl)-1-cyclohexene and that in Renilla is a tryptamine derivative that has not yet been accurately identified; the luciferins of other luminescent organisms are not yet known. A review is given of the investigations which have been carried out on the above luciferins and the course of the luciferin-luciferase reaction is examined. Numerous spectral data obtained during the examination of these compounds are included in the text. 相似文献
166.
The macrocyclic core of gymnodimine has been constructed via an intramolecular Diels-Alder reaction of an alpha,beta-unsaturated iminium dienophile in water. The cycloaddition furnished a single exo-product, along with two endo-products. Through X-ray analysis of a suitable derivative, the stereochemistry of the exo-product was established, thereby demonstrating that its stereochemistry matches that of gymnodimine. In contrast, macrocyclization of an analogous alpha,beta-unsaturated ketone dienophile gave only undesired endo-products. Interestingly, the imine dienophile shows remarkable stability in water. [reaction: see text] 相似文献
167.
Sasaki H Yonekubo J Kanai M Toriba A Kizu R Hayakawa K 《Biomedical chromatography : BMC》2002,16(7):432-436
A liquid chromatographic (LC) method has been developed for the separation of 11 monohydroxybenzo[a]pyrenes (OH BaPs) positional isomers, and for their detection using electrospray ionization mass spectrometry (ESI-MS). All OH BaPs isomers were separated on an octadecylsilyl (C(18))-bonded amorphous organosilica column utilizing gradient elution with acetonitrile-water and triethylamine (TEA) at pH 11.0 and determined by MS, except 2- and 8-OH BaPs which were coeluted. The lower detection limits were in the range from 1.6 micro g/L for 12-OH BaP to 12 micro g/L for 5-OH BaP without any sample enrichment. The relative standard deviations of area response were in the range from 1.8% (9-OH BaP) to 4.9% (12-OH BaP) except for 9.4% (7-OH BaP). The developed method was successfully applied to incubation mixtures of BaP and CYP1A1/epoxide hydrolase. This method identified 1-, 3- and 9-OH BaPs as the major metabolites, and 2- (and/or 8-) and 12-OH BaPs as the minor metabolites in the incubation mixture. 相似文献
168.
[reaction: see text] N-Tosyl 3-substituted indoles were hydrogenated with high enantioselectivities (95-98% ee) by use of a trans-chelating chiral bisphosphine, (S,S)-(R,R)-PhTRAP ligand. The chiral catalyst, which was generated in situ from [Rh(nbd)(2)]SbF(6), PhTRAP, and Cs(2)CO(3), is useful for enantioselectively synthesizing a range of diverse optically active indolines possessing a chiral carbon at the 3-position. 相似文献
169.
Benzoins are simply oxidized to benzils in excellent yields with a catalytic amount of triarylstibanes under an aerobic condition. This catalytic oxidation is heteroatom-specific in the antimony compound and no reaction take place with other group 15 reagents such as triphenylphosphane, -arsane and -bismuthane. The reaction should involve an oxidation-reduction cycle between stibane Sb(III) and stiborane Sb(V) under air. 相似文献
170.
[structure: see text] Stereoselective total synthesis of scytophycin C, a marine 22-membered macrolide displaying potent activity against a variety of human carcinoma cell lines, has been reported in which the polypropionate structure bearing contiguous asymmetric centers was stereospecifically constructed by using new acyclic stereocontrol. This paper describes stereoselective syntheses of the C(1)-C(18) segment (Segment A) including a trans-disubstituted dihydropyran ring and the C(19)-C(31) segment (Segment B) having eight stereogenic centers. 相似文献