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排序方式: 共有484条查询结果,搜索用时 15 毫秒
431.
[RuCl2(CO)3]2 catalyzes intermolecular cyclopropanation of various alkenes with propargylic acetates to give vinylcycloropanes in good yields. The key intermediate of this reaction is a vinylcarbene complex generated by nucleophilic attack of the carbonyl oxygen of the acetate to an internal carbon of alkyne activated by the ruthenium complex. 相似文献
432.
Maeda Y Kakiuchi N Matsumura S Nishimura T Kawamura T Uemura S 《The Journal of organic chemistry》2002,67(19):6718-6724
A catalytic system consisting of vanadium oxyacetylacetonate [VO(acac)(2)] and 3 A molecular sieves (MS3A) in acetonitrile works effectively for the aerobic oxidation of propargylic alcohols [R(1)CH(OH)Ctbd1;CR(2)] to the corresponding carbonyl compounds under an atmospheric pressure of molecular oxygen. Although the reactivity of alpha-acetylenic alkanols (R(1) = alkyl) is lower compared to that of the alcohols of R(1) = aryl, alkenyl, and alkynyl, the use of VO(hfac)(2) as a catalyst and the addition of hexafluoroacetylacetone improve the product yield in these cases. A catalytic cycle involving a vanadium(V) alcoholate species and beta-hydrogen elimination from it has been proposed for this oxidation. 相似文献
433.
[reaction: see text] The reaction of alkenes with conjugated ene-yne-imino ether or ene-yne-aldimine in the presence of a catalytic amount of [Rh(OAc)(2)](2) gives (2-pyrrolyl)cyclopropanes in good yields. The key intermediate of this cyclopropanation is a (2-pyrrolyl)carbenoid generated by the nucleophilic attack of imine nitrogen atom at an internal alkyne carbon activated by rhodium complex. The intramolecular reaction also proceeds to afford a polycyclic pyrrole. 相似文献
434.
H Toyoda S Yamanashi Y Hakamada K Shinomiya T Imanari 《Chemical & pharmaceutical bulletin》1989,37(6):1627-1628
A highly sensitive high-performance liquid chromatographic method with fluorometric postcolumn labeling using 2-cyanoacetamide was developed for the profile analysis of chondroitin sulfates (ChS) in normal human urine and serum. Over-sulfated disaccharide units such as di- or trisulfated unsaturated disaccharides in urine were estimated and unsaturated 6-sulfated disaccharide (delta Di-6S) was found as a major component from ChS in urine, although only small amounts of delta Di-6S from ChS were present in serum. 相似文献
435.
Characterization of contaminants in EMS-associated L-tryptophan samples by high-performance liquid chromatography 总被引:2,自引:0,他引:2
T Toyo'oka T Yamazaki T Tanimoto K Sato M Sato M Toyoda M Ishibashi K Yoshihira M Uchiyama 《Chemical & pharmaceutical bulletin》1991,39(3):820-822
To identify chemical contaminant(s) associated with eosinophilia-myalgia syndrome (EMS), case and control lots of tryptophan were analyzed by HPLC with both UV and FL detection. Numerous contaminant peaks appeared on the chromatograms and some of them were identified as 5-hydroxytryptophan, indol aldehyde, indol, etc; from the retention time of authentic compounds. Among these, three peaks were significantly associated with case lots. One corresponds to di-tryptophan aminal of aldehyde (peak E). Others are unknown contaminants, UV-5 (FL-7) and UV-28 (FL-36). The structural elucidation and toxicological implication of UV-5 (FL-7) are currently in progress. 相似文献
436.
Functionalized poly(ethylene oxide) (PEO) macromonomers (alpha -tertiary amino and omega -methacryloyl groups) were prepared by ring-opening polymerization of live PEO anions end-capped with styrene oxide using 2-[2-(N ,N -dimethylamino)-ethoxy]ethanol potassium alkoxides as an initiator with methacryloyl chloride. PEO brushes were synthesized by free-radical homopolymerization of such PEO macromonomers. These brushes were converted into peripherally charged brushes by quaternization. We studied the solution properties of both types of brushes from the viewpoint of charge effect. It was found from dynamic light scattering (DLS) that the polymer brushes formed a single macromolecule in solution due to crowding of side chains. It was speculated from angular dependence measurements that the polymer brushes with large aspect ratios took a geometrical anisotropic conformation such as a cylinder. In methanol with a low dielectric constant, radius of gyration (R(G)), and cross-sectional radius of gyration (R(G,C)) of the polymer brushes with charged side chains were smaller than those of the polymer brushes without charges. In a solvent with a low dielectric constant such as methanol, ionic groups do not dissociate and condense. On the other hand, these physical values in an aqueous solution were somewhat larger than those of the polymer brushes without charges. In water with a high dielectric constant, peripherally charged brushes were strongly stabilized by electric double layers. 相似文献
437.
Ichikawa M Takahashi M Aoyagi S Kibayashi C 《Journal of the American Chemical Society》2004,126(50):16553-16558
The first total syntheses of new monoterpene alkaloids (-)-incarvilline, (+)-incarvine C, and (-)-incarvillateine, corresponding to the natural enantiomers, have been accomplished. The strategy for the synthesis of these natural products utilized 6-epi-incarvilline as a common precursor, which was assembled by a three-component coupling reaction using (4S)-4-siloxy-2-cyclopenten-1-one to construct an appropriately trisubstituted cyclopentanone, followed by ring closure to the cis-perhydro-2-pyrindine skeleton by means of a reductive Heck-type reaction. Furthermore, topochemically controlled [2 + 2] photodimerization of cinnamic acid derivatives in the solid state for the stereospecific construction of a 1,2,3,4-tetrasubstituted cyclobutane ring was also investigated as a means to access (-)-incarvillateine. 相似文献
438.
Palladium-catalyzed transformation of cyclobutanone O-benzoyloximes to a variety of nitriles is described. The reaction may proceed via two important steps, that is, (i) oxidative addition of the N-O bond of oximes to Pd(0) to give a cyclobutylideneaminopalladium(II) species and (ii) beta-carbon elimination of this species to afford a reactive alkylpalladium species. The kind of products is very dependent on the nature of substituents on the cyclobutane ring. The direction of the C-C bond cleavage is controlled by the kind of ligand employed. The sequential reaction composed of the C-C bond cleavage and the subsequent intra- and intermolecular C-C bond formations via the corresponding alkylpalladium species is also demonstrated. For example, an oxime having an alkynyl moiety at a suitable position reacts with a variety of alkenes to afford nitriles bearing dienylcyclopentane moiety in moderate to good yields. 相似文献
439.
Intermolecular cyclopropanation reactions of various alkenes with propargylic carboxylates 1 are catalyzed by [RuCl2(CO)3]2 to give vinylcyclopropanes 2 in good yields. The key intermediate of the reaction is a vinylcarbene complex generated in situ by nucleophilic attack of a carbonyl oxygen of the carboxylates to an internal carbon of the alkyne activated by the ruthenium complex. A variety of transition-metal compounds other than the Ru compound can also be employed in this system. Similar cyclopropanation proceeds with conjugated dienes as well to give trans-vic-divinylcyclopropane derivatives and cycloheptadiene derivatives 5, the latter being thermally derived from the initially formed cis-vic-isomers via Cope-type rearrangement. The present reaction is chemically equivalent to the transition metal-catalyzed cyclopropanation reaction using alpha-diazoketones as carbenoid precursors. 相似文献
440.
A very short and efficient enantioselective total synthesis of the tricyclic marine alkaloids (-)-lepadiformine (3), (+)-cylindricine C (1c), and (-)-fasicularin (4) has been developed utilizing the formyloxy 1-azaspiro[4.5]decane 5 as a common intermediate. The key strategic element for the synthesis was the formic acid-induced intramolecular conjugate azaspirocyclization, which proved to be a highly efficient and stereoselective way to rapid construction of the 1-azaspirocyclic substructure of these natural products in a single operation. Thus, the common intermediate 5, synthesized in two steps with 70% overall yield starting from the known (S)-N-Boc-2-pyrrolidinone 7 via the conjugate spirocyclization using an acyclic ketoamide 6, was utilized for the concise and stereoselective total synthesis of (-)-lepadiformine (3), which was accomplished in seven steps with 45% overall yield from 5 (31% yield from 7). The developed strategy based on the conjugate spirocyclization was also applied to the stereoselective total synthesis of (+)-cylindricine C (1c), which was achieved in 10 steps from 5 in 18% overall yield (12% yield from 7). Further application of this approach using 5 led to the synthesis of (-)-fasicularin (4), wherein an extremely efficient method for the introduction of the thiocyanato group via an aziridinium intermediate at the last step was developed. Thus, the highly efficient first enantioselective total synthesis of (-)-fasicularin was accomplished in nine steps with an overall yield of 41% from 5 (28% yield from 7). 相似文献