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11.
N-(omega-Bromoalkyl)-amino acid derivatives, readily prepared from natural alpha-amino acids, gave cyclic amino acids with a quaternary stereocenter by treatment with potassium hexamethyldisilazaide in DMF. The chirality of parent amino acids was almost completely preserved during an enolate-formation and cyclization process, giving aza-cyclic amino acids in up to 98% ee in retention of configuration. This method is applicable to the asymmetric synthesis of azetidine, pyrrolidine, piperidine, and azepane derivatives. The asymmetric cyclization seems to proceed via an axially chiral enolate intermediate and not through a concerted SEi process. 相似文献
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A density-functional theory is presented to study the structure of polymers, having attractive interactions, confined between attractive surfaces. The theory treats the ideal-gas free-energy functional exactly and uses weighted density approximation for the hard-chain contribution to the excess free-energy functional. The bulk interactions of freely jointed hard spheres are obtained from generalized Flory equation of state and the attractive interactions are calculated using the direct correlation function obtained from the polymer reference interaction site model theory along with the mean spherical approximation closure. The theoretical predictions are found to be in quite good agreement with the Monte Carlo simulation results for varying densities, chain lengths, and different interaction potentials. The results confirm important implications of using different approximations for the hard-sphere and attractive interactions. 相似文献
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Ratna Dasgupta Pranab R. Kanjilal Swapan K. Patra Manish Sarkar Usha Ranjan Ghatak 《Tetrahedron》1985,41(23):5619-5625
The efficacy of a new acid-catalyzed intramolecular C-alkylation has been demonstrated by the synthesis of 1-methyl-4--methoxyphenylbicyclo [2.2.2] octan-2-one () and 4--methoxyphenylbicyclo [2.2.2] octan-2-one () from easily accessible starting materials. The carbinol , derived from , undergoes facile rearrangement leading to 1--methoxyphenyl-4-methyl bicyclo [3.2.1] oct-3-ene (), which has been transformed to -1--methoxyphenyl-4-methylbicyclo [3.2.1] octan-3-one (). 相似文献
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Ambarish Mondal Rajat K. Tripathy Parul Dutta Manas Kumar Santra Anvarhusein A. Isab Christopher W. Bielawski Hemanta K. Kisan Swapan K. Chandra Joydev Dinda 《应用有机金属化学》2019,33(1)
The syntheses, structures, and chemotherapeutic activities of Ag(I)‐, Au(I)‐, and Ru(II)‐complexes ligated to a novel N‐heterocyclic carbene ligand, 2‐(4‐nitrophenyl)imidazo[1,5‐a]pyridin‐2‐ylidene ( 1 ), are described. The corresponding complexes, [Ag( 1 )2][PF6], [Au( 1 )2][PF6] ( 3 ), and [Ru( 1 )(p‐cymene)Cl][PF6] ( 4 ), were prepared using convenient transmetallation chemistry and characterized using a range of spectroscopic and analytical techniques. X‐ray crystallography revealed that complexes 2 and 3 adopted linear structures whereas 4 exhibited a prototypical “piano‐stool”‐like geometry; the structural assignments were further supported by DFT calculations. A series of in vitro studies revealed that while the aforementioned Ag(I), Au(I) and Ru(II) complexes exhibited significant cytotoxicities against the human colon adenocarcinoma (HCT 116), lung cancer (A549), and breast cancer (MCF7) cell lines, the Ru derivative was most prominent. 相似文献
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The polymer-cement composite is an immiscible band having modified morphology. Polymer phase improves the toughness of brittle cement and has a reinforcing effect, and interactions between cement components and polymers provide stability. In this study, polymer latex [poly(methyl methacrylate), PMMA] – cement paste was prepared with different weight proportions of polymer content. The main scientific objective of this report has been the analysis and the prediction of high strength with the aim of understanding the interactions of PMMA polymer with Portland cement after hydration reaction of cement pastes and curing the specimens for 28 days. The samples were studied by Fourier transform infrared (FT-IR) spectroscopy. The results are critically examined. It is shown that bands support the interaction of PMMA with cement in the composite. 相似文献