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241.
Robert J. Rosenthal Richard T. Carl John P. Beauchaine Michael P. Fuller 《Mikrochimica acta》1988,95(1-6):149-153
Quantitative photoacoustic and transmission infrared spectroscopy have been compared for a highly overlapped three component mixture with concentrations varying from 0 to 60%. A partial leastsquares model has been employed for the quantitative analysis. High correlation coefficients were obtained for both the transmission and photoacoustic model. 相似文献
242.
We have demonstrated that the high yields and selectivities of 1,3-dipolar cycloadditions can be translated into facile stereoselective syntheses of a diverse array of beta-amino acids, key components of bioactive natural products, beta-lactams, and peptidomimetics. Simply by selecting different combinations of three readily available starting materials (an oxime, a chiral allylic alcohol, and a nucleophile), we used the reaction sequence to prepare four different beta-amino acid structural types with a variety of substitution patterns in good overall yield. Of particular note is the use of this approach to prepare highly substituted beta-amino acids not readily accessible by previously reported methodologies. This will pave the way for future studies of the structure and function of this important class of molecules. 相似文献
243.
beta-Amino acids are important synthetic targets due to their presence in a wide variety of natural products, pharmaceutical agents, and mimics of protein structural motifs. While beta-amino acids containing geminal substitution patterns have enormous potential for application in these contexts, synthetic challenges to the stereoselective preparation of this class of compound have thus far limited more complete studies. We present here a straightforward method employing chiral isoxazolines as key intermediates to access five different beta-amino acid structural types with excellent selectivity. Of particular note is the use of this approach to prepare highly substituted cis-beta-proline analogues. The ready access to these diversely substituted compounds is expected to facilitate future studies of the structure and function of this important class of molecules. 相似文献
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247.
Kilian P Parveen S Fuller AL Slawin AM Derek Woollins J 《Dalton transactions (Cambridge, England : 2003)》2008,(14):1908-1916
Reaction of naphthalene-1.8-bis(dichlorophosphine) with sodium selenide and selenium gives naphthalene-1,8-diyl)-1,3,2,4-diselenoxodiphosphetane 2,4-diselenide (27), a molecule with its four-membered PSePSe ring spanned by a naphthalene-1,8-diyl backbone. 27 was fully characterised, including by X-ray diffraction. Unusually, the reaction yielded not only 27, but also a polymeric or oligomeric material that was selenium deficient, containing significant amount of species with phosphorus atoms not fully oxidised to P(V). Reactions of the selenium deficient material with simple alcohols afforded two 1,2-diphosphaacenaphthenes, which were structurally characterised. 相似文献
248.
The de novo synthesis of small organic heterocyclic molecules has benefited from recent protocols for copper-facilitated additions of heteroatoms to alkenes, alkynes and arenes. This tutorial review summarizes a number of these recent contributions. Copper salts can facilitate bond formations due to their ability to serve as Lewis acids, oxidizing agents and transition metal catalysts. The current understanding of the mechanisms of these reactions is presented. This review should be of interest to chemists involved in the synthesis of heterocycles and those investigating transition metal facilitated reactions. 相似文献
249.
Monteux C Jung E Fuller GG 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3975-3980
We report surface pressure-area (Pi-A) isotherms of bidisperse mixtures of anionic polystyrene latex particles at a water/n-decane interface as well as optical photographs of the interface for various compressions and mixture ratios. In the case of mixtures of 3 and 5 mum particles, we observe crystalline layers at high or low concentration ratios, where the "impurity" particles concentrate at the grain boundaries of the crystalline structure. At intermediate ratios, the layers become highly disordered. However, in both cases, we show that the shape of the isotherms remains unchanged. In the case of the mixtures of 9 mum particles with either 3 or 5 mum particles, the smaller particles aggregate around the larger particles through capillary interaction resulting in the formation of large fractal aggregates. At high compression, these layers contain holes that seem very compressible. As a result, the surface pressure isotherms show a smaller surface pressure jump than for other mixtures. 相似文献
250.
An expanded substrate scope and in-depth analysis of the reaction mechanism of the copper(II) carboxylate-promoted intramolecular carboamination of unactivated alkenes is described. This method provides access to N-functionalized pyrrolidines and piperidines. Both aromatic and aliphatic gamma- and delta-alkenyl N-arylsulfonamides undergo the oxidative cyclization reaction efficiently. N-Benzoyl-2-allylaniline also underwent the oxidative cyclization. The terminal olefin substrates examined were more reactive than those with internal olefins, and the latter terminated in elimination rather than carbon-carbon bond formation. The efficiency of the reaction was enhanced by the use of more organic soluble copper(II) carboxylate salts, copper(II) neodecanoate in particular. The reaction times were reduced by the use of microwave heating. High levels of diastereoselectivity were observed in the synthesis of 2,5-disubstituted pyrrolidines, wherein the cis substitution pattern predominates. The mechanism of the reaction is discussed in the context of the observed reactivity and in comparison to analogous reactions promoted by other reagents and conditions. Our evidence supports a mechanism wherein the N-C bond is formed via intramolecular syn aminocupration and the C-C bond is formed via intramolecular addition of a primary carbon radical to an aromatic ring. 相似文献