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81.
Stockman RA Sinclair A Arini LG Szeto P Hughes DL 《The Journal of organic chemistry》2004,69(5):1598-1602
An entirely two-directional synthesis of (+/-)-perhydrohistrionicotoxin is presented, utilizing a tandem oxime formation/Michael addition/[3 + 2] cycloaddition as the key step. This approach also constitutes formal syntheses of (+/-)-histrionicotoxin and (+/-)-histrionicotoxin 235A. 相似文献
82.
Daniel Erne Daniel Ammann Alex F. Zhukov Felix Behm Ern Pretsch Wilthelm Simon 《Helvetica chimica acta》1982,65(2):538-545
A series of lipophilic N, N, N′,N′-tetrasubstituted diamides were prepared and their selectivity in solvent polymeric membranes was studied, cis-N, N, N′, N′-Tetraisobutylcyclohexane-1,2-dicarboxamide induces a selectivity in membranes for Li+over alkaline earth metal cations and other alkali metal cations by a factor of about 1000 and 100 respectively. The ionophore N, N′-diheptyl-N,N′-dimethylethylmalonamide is an attractive candidate for the use in microelectrodes for the determination of intracellular Mg2+-activities. 相似文献
83.
Copper mediated allylic substitutions and conjugate additions to geranyl, cinnamyl and allylic indole compounds have been investigated with the aim of finding a method for the creation of the all-carbon quaternary centre present in the natural product lyngbyatoxin A. Reaction conditions have been found giving a 68% SN2' selectivity in the copper mediated addition of PhMgBr to geranyl chloride, as well as 99% and 95% SN2' selectivity in the copper catalysed addition of EtMgBr to cinnamyl chloride and acetate, respectively. When the optimised reaction conditions were applied to the corresponding allylic compounds containing a 7-substituted indole moiety, the regioselectivity was reversed giving only the SN2 product. The allylic indole-containing substrates were also found to be unproductive in Pd- or Mo-catalysed SN2'-type substitution reactions. In related studies, copper catalysed conjugate addition of EtMgBr to the tricyclic lactam 6-methyl-pyrrolo[3,2,1-ij]quinolin-4-one gave a maximum of 20% of the 1,4-addition product. 相似文献
84.
85.
Molecular dynamics simulations have been used to study the spontaneous aggregation of a concentrated solution of dipalmitoylphosphatidylcholine (DPPC) molecules in water into a small vesicle. The molecules were represented in atomistic detail. Starting from a DPPC solution in water, an oblong vesicle with a long axis of 15 nm and short axes of 10 nm was formed spontaneously. After 90 ns of simulation, the vesicle contained a number of water pores. Water pores were shown to facilitate exchange of lipids between inner and outer leaflets. Lipid tails were shown to be less ordered in the inner leaflet of the vesicle, as compared to those in the outer leaflet of the vesicle and an equilibrated lamellar bilayer. 相似文献
86.
Beattie JK Djerdjev AM Franks GV Warr GG 《The journal of physical chemistry. B》2005,109(33):15675-15676
Homogenization of hexadecane in water at pH 9 gives the same surface charge density in the presence of 0.2 mM thiocyanate or acetate anions as in the presence of chloride, indicating that these dipolar anions are not preferentially adsorbed at the oil/water interface. The decrease in the zeta potential of the emulsion droplets as the sodium salts of iodate, thiocyanate, or acetate are added from 0.1 to 10 mM is the same as that when sodium chloride is added, leading to the same conclusion. Increasing the sodium hydroxide concentration from pH 9 to 11.5 has a different effect on the zeta potential, consistent with the specific adsorption of hydroxide ion at the oil/water interface. 相似文献
87.
A set of isomeric para- and meta-trimethylsilylphenyl ortho-substituted N,N-phenyl α-diimine ligands [(Ar-NC(Me)-(Me)CN-Ar) Ar=2,6-di(4-trimethylsilylphenyl)phenyl (16); Ar=2,6-di(3-trimethylsilylphenyl)phenyl (17)] have been synthesized through a two-step procedure. The palladium-catalysed cross-coupling reaction between 2,6-dibromophenylamine (7) and 4-trimethylsilylphenylboronic acid (8), 3-trimethylsilylphenylboronic acid (9) was used to prepare 4,4′-bis(trimethylsilyl)-[1,1′;3′,1″]terphenyl-2′-ylamine (10) and 3,3′-bis(trimethylsilyl)-[1,1′;3′,1″]terphenyl-2′-ylamine (11). The di-1-adamantylphosphine oxide Ad2P(O)H (13) and di-tert-butyl-trimethylsilylanylmethylphosphine tert-Bu2P-CH2-SiMe3 (14) were used for the first time as ligands for the Suzuki coupling. The condensation of 2,2,3,3-tetramethoxybutane (15) with anilines 10 and 11 afforded α-diimines 16 and 17. The reaction of π-allylnickel chloride dimer (18), α-diimines (16), (17) and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAF) (19) or silver hexafluoroantimonate (20) led to two sets of isomeric complexes [η3-allyl(Ar-NC(Me)-(Me)CN-Ar)Ni]+ X−, [Ar=2,6-di(4-trimethylsilylphenyl)phenyl, X=BAF (3), X=SbF6 (4); Ar=2,6-di(3-trimethylsilylphenyl)phenyl, X=BAF (5), X=SbF6 (6)]. The steric repulsion of closely positioned trimethylsilyl groups in 4 caused the distortion of the nickel square planar coordination by 17.6° according to X-ray analysis. 相似文献
88.
Synthesis of radioactive α-melanotropin derivatives containing a bromoacetyl or diazoacetyl group for studies of covalent hormone-macromolecule complexes α-Melanotropin derivatives and fragments covalently bound to human serum albumin through their N-terminal end exhibit almost the same biological activity as the corresponding free Nα-acetylated peptides [6]. The preparation of such complexes requires derivatives with a ‘reactive’ N-terminal acetyl group. We describe here the synthesis of three α-melanotropin fragments and of two specifically tritiated α-melanotropin derivatives containing Nα-bromoacetyl or Nα-diazoacetyl groups: BrCH2CO · Glu-His-Phe-Arg-Trp-Gly-Lys-Pro-Val · NH2, BrCH2CO · Glu-His-Phe-Arg-Trp-Gly · OH, BrCH2CO · Trp-Gly-Lys-Pro-Val middot; NH2, BrCH2CO · D -Ala-Tyr(3H2)-Gly-Nva-Glu-His-Phe-Arg-Trp-Gly-Lys-Pro-Val · NH2, and N2 = CHCO · Gly-Tyr(3H2)-Ser-Nva-Glu-His-Phe-Arg-Trp-Gly- Lys-Pro-Val · NH2. The latter two analogues displayed a specific radioactivity of about 20 and 36 Ci/mmol, and a biological activity of 2 · 109 and 6 · 109 U/mmol respectively. They are also being used for affinity and photoaffinity labelling of receptor molecules and antibody combining sites. 相似文献
89.
The preparation and identification of a series of trifluoromethylated and bis(trifluoromethylated) precursors and monomers for bridge substituted trifluoromethylated poly(p-phenylenevinylene) (PPV) is reported. These monomers were prepared in several steps from terephthaldicarboxaldehyde and they contain symmetrical and unsymmetrical combinations of leaving groups and/or polarizers, including chlorides, sulfoxides, sulphones, tosylates and S-methyl (and also O-ethyl) xanthates. The electron withdrawing effect of the trifluoromethyl group dominated the regioselectivity of substitution, thus allowing the convenient and selective formation of unsymmetrically substituted products in high yield. 相似文献
90.
Whittle M Gillet VJ Willett P Alex A Loesel J 《Journal of chemical information and computer sciences》2004,44(5):1840-1848
This paper evaluates the effectiveness of various similarity coefficients for 2D similarity searching when multiple bioactive target structures are available. Similarity searches using several different activity classes within the MDL Drug Data Report and the Dictionary of Natural Products databases are performed using BCI 2D fingerprints. Using data fusion techniques to combine the resulting nearest neighbor lists we obtain group recall results which, in many cases, are a considerable improvement on standard average recall values obtained for individual structures. It is shown that the degree of improvement can be related to the structural diversity of the activity class that is searched for, the best results being found for the most diverse groups. The group recall of active compounds using subsets of the class is also investigated: for highly self-similar activity classes, the group recall improvement saturates well before the full activity class size is reached. A rough correlation is found between the relative improvement using the group recall and the square of the number of unique compounds available in all of the merged lists. The Tanimoto coefficient is found unambiguously to be the best coefficient to use for the recovery of active compounds using multiple targets. Furthermore, when using the Tanimoto coefficient, the "MAX" fusion rule is found to be more effective than the "SUM" rule for the combination of similarity searches from multiple targets. The use of group recall can lead to improved enrichment in database searches and virtual screening. 相似文献