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71.
Okada Y Yokozawa M Akiba M Oishi K O-kawa K Akeboshi T Kawamura Y Inokuma S Nakamura Y Nishimura J 《Organic & biomolecular chemistry》2003,1(14):2506-2511
A variety of aromatic compounds with both activating and deactivating substituents were brominated with sodium monobromoisocyanurate (SMBI) 1, diethyl ether, diethyl ether-methanesulfonic acid, trifluoroacetic acid, or sulfuric acid were employed as solvents. Thus nitrobenzene was conveniently brominated in sulfuric acid, benzene was readily monobrominated in diethyl ether-methanesulfonic acid, and phenol was selectively brominated at the ortho position under mild conditions in refluxing diethyl ether. With substituents that are easily protonated, trifluoroacetic acid may be employed as solvent in the reaction with 1, in contrast NBS was ineffective in trifluoroacetic acid. This renders 1 a superior reagent relative to NBS. In addition to aromatics, alkenes, ketones and esters were also brominated with 1. Diethyl malonate was brominated with 1 and then subjected to a Bingel reaction with NaH to afford the desired methanofullerene in reasonable yield. 相似文献
72.
The partial molar free energy, enthalpy, and entropy of oxygen in niobium oxides with ratios from 2.47 to 2.50 were measured with a galvanic cell in the temperature range from 1084 to 1325 K. The partial molar enthalpies of oxygen of the Nb2O5?x and V phases were observed to be nearly independent of composition, indicating the presence of only weak interactions between defects. The value of the slope for the plots of log x in Nb2O5?x against log PO2 was observed to be which is interpreted in terms of a defect structure involving both singly ionized and doubly ionized oxygen vacancies. The previously proposed phase diagram in the vicinity of Nb2O5?x was confirmed by the present emf measurements. 相似文献
73.
74.
Various computational approaches, using molecular mechanics (Amber), semiempirical (AM1), density functional (B3LYP), and various ONIOM methods, have been comparatively investigated for the structure of Escherichia coli NifS CsdB protein. The structure of the entire monomer containing 407 amino acid residues and 579 surrounding water molecules has been optimized. The full geometry optimization in the "active site-only" approach (including only active site atoms) has been found to give the largest root-mean-square (RMS) deviation from the X-ray structure; a much better agreement has been achieved by keeping the atoms leading to the backbones of some amino acids frozen in their positions in the X-ray structure. The best agreement has been attained by including the surrounding protein in the calculations using the two-layer ONIOM (B3LYP:Amber) approach. The results presented in this study conclusively demonstrate the importance of the protein/active-site interaction on the active-site structure of the enzyme. The present theoretical study represents the largest system studied at the ONIOM level to date, containing 7992 atoms, including 84 atoms in the QM region and rest in the MM region. 相似文献
75.
76.
Hirai A Matsui A Komatsu K Tanino K Miyashita M 《Chemical communications (Cambridge, England)》2002,(17):1970-1971
A highly regio- and stereoselective alpha-methylation reaction of gamma,delta-epoxy-alpha,beta-unsaturated esters was achieved by using a Me2Zn-CuCN reagent. 相似文献
77.
Characterization of clarithromycin polymorph was performed by solid-state cross polarization and magic angle spinning (CP/MAS) 13C-NMR spectroscopy. Two polymorphs, form II and form I, of clarithromycins indicated characteristic resonances of C1 carbonyl carbon at 176.2 and 175.2 ppm, respectively. Since each peak of C1 carbon was well separated in the spectrum of the two polymorphs, we performed quantitative analysis of the polymorphic fraction from the peak area of these peaks. The peak area of form I was found to linearly increase with an increase of its content, with a correlation coefficient of above 0.99. Solid-state NMR was found to be a useful technique to determine the characteristics of the polymorphic forms. 相似文献
78.
Majima K Takita R Okada A Ohshima T Shibasaki M 《Journal of the American Chemical Society》2003,125(51):15837-15845
We describe the development of a general catalytic asymmetric Michael reaction of acyclic beta-keto esters to cyclic enones, in which asymmetric induction occurs at the beta-position of the acceptors. Among the various asymmetric catalyst systems examined, the newly developed La-NR-linked-BINOL complexes (R = H or Me) afforded the best results in terms of reactivity and selectivity. In general, the NMe ligand 2 was suitable for the combination of small enones and small beta-keto esters, and the NH ligand 1 was suitable for bulkier substrates (steric tuning of the catalyst). Using the La-NMe-linked-BINOL complex, the Michael reaction of methyl acetoacetate (8a) to 2-cyclohexen-1-one (7b) gave the corresponding Michael adduct 9ba in 82% yield and 92% ee. The linker heteroatom in linked-BINOL is crucial for achieving high reactivity and selectivity in the Michael reaction of beta-keto esters. The amine moiety in the NR-linked-BINOL can also tune the Lewis acidity of the central metal (electronic tuning of the catalyst), which was supported by density functional studies and experimental results. Another advantage of the NR-linked-BINOL ligand as compared with O-linked-BINOL is the ease of modifying a substituent on the amine moiety, making it possible to synthesize a variety of NR-linked-BINOL ligands for further improvement or development of new asymmetric catalyses by introducing additional functionality on the linker with the amine moiety. The efficiency of the present asymmetric catalysis was demonstrated by the synthesis of the key intermediate of (-)-tubifolidine and (-)-19,20-dihydroakuammicine in only five steps compared to the nine steps required by the original process from the Michael product of malonate. This strategy is much more atom economical. On the basis of the results of mechanistic studies, we propose that a beta-keto ester serves as a ligand as well as a substrate and at least one beta-keto ester should be included in the active catalyst complex. Further improvement of the reaction by maintaining an appropriate ratio of the La-NMe-linked-BINOL complex and beta-keto esters is also described. 相似文献
79.
A sample solution containing sodium or potassium dihydrogenphosphate or disodium or dipotassium hydrogenphosphate was eluted from a Sephadex G-15 column with either sodium or potassium chloride solution in various sample-eluent systems, and every one of the four kinds of ions employed was determined in the eluate. Then, the elution profiles showed the phenomenon that a negative peak of chloride ion coexisted in the fractions of a positive peak of phosphate ion, in all sample-eluent systems employed. This phenomenon was assumed to occur by the coupled reaction of change-partner and ion-exchange reactions including ion exclusion. 相似文献
80.
[reaction: see text] A concise and enantioselective synthesis of (S)-2-cyclohexyl-2-phenylglycolic acid as a key intermediate for (S)-oxybutynin is reported. The crucial asymmetric tetrasubstituted carbon center was constructed with excellent stereoselectivity through the proline-catalyzed direct asymmetric aldol reaction between cyclohexanone and ethyl phenylglyoxylate under mild conditions. 相似文献