Molecular, 1D,and 2D systems built from phenylcyanamido ligands. Syntheses,crystal structures,and characterization of their magnetic properties

Several MnII compounds with phenylcyanamido ligands have been synthesized and characterized by means of single-crystal X-ray structural determination. The reported compounds show a wide variety of nuclearity from mononuclear and dinuclear systems to 1D chains and 2D networks in which X-phenylcyanamide (X-pcyd) anions act as the bridging ligand. Mononuclear compound [Mn(H2O)2(4-bzpy)2(3-Cl- pcyd)2] (2) crystallizes in the monoclinic system, P21/a space group, dinuclear compounds (mu 1,3-3-Cl-pcyd)2[Mn(2,2'-bpy)(3-Cl-pcyd)(MeOH)]2 (2) and (mu 1,3-3-Cl-pcyd)2[Mn(2,2'-bpy)(3-Cl-pcyd)(EtOH)]2 (3) crystallize in the triclinic system, P1 space group, 1D chain [(mu 1,3-4-Cl-pcyd)2[Mn(2,2'-bpy)]]n (4) crystallizes in the monoclinic system, /2/a space group, and 2D network [Mn(mu-4,4'-bpy)(mu 1,3-3-F-pcyd)2]n (5) crystallizes in the monoclinic system, C2 space group. Susceptibility measurements on compounds 2-4 reveal moderate antiferromagnetic coupling in all cases. MO calculations have been made to elucidate the main factors that control the superexchange pathway for this kind of ligand. Comparison of their magnetic behavior with that of related ligands such as azido and dicyanamido is reported.     

New Adamantane Derivatives with NO-Generating Fragment

An approach to the synthesis of adamantane derivatives with NO-generating fragment containing nitroxy group has been developed. 1-Aminoadamantane, memantine, and adamantanecarboxylic acid have been used as initial compounds. The prepared compounds have shown ability to generate nitric oxide in a system mimicking biological reactions of nitro group reduction.     

有机铝化合物的结构对丙烯齐聚均相催化剂性能的影响

在常用的过渡金属络合物——有机铝化合物(或再加路易士酸碱作为第三组份)的均相体系中,改变络合物配体的研究做得比较多,而有机铝化合物的结构的改变对催化剂性能的影响见于报道的十分有限。本文就以甲苯为溶剂的Ni(acac)_2/Et_2AlY均相体系中,通过选择具有不同结构特点的Y,研究铝化合物结构对催化剂性能的影响。     

Fluorescent detection of carbon-carbon bond formation

We have developed a new spectroscopic system for detecting carbon-carbon bond formation by fluorescence to enhance high-throughput catalyst screening and rapid characterization of catalysts on a small scale. Fluorogenic substrates composed of a fluorophore possessing an amino group are readily prepared as amides of alpha,beta-unsaturated carbonyl compounds and generally exhibit low fluorescence, while Michael or Diels-Alder reactions of these fluorogenic substrates provide products of significantly increased fluorescence. The product's fluorescence is approximately 20- to 100-fold higher than that of the substrate. The assay system was validated by screening potential catalysts of the Michael reaction and in solvent optimization experiments. The covalent combination of fluorophores possessing an amino group with alpha,beta-unsaturated carbonyl compounds should provide a diverse range of fluorogenic substrates that may be used to rapidly screen catalysts and to optimize reaction conditions.     

Chemical assay-guided natural product isolation via solid-supported chemodosimetric fluorescent probe

As a new model of chemical assay-guided natural product isolation, an effective chemodosimetric assay system was devised. Our chemical assay system features a fluorogenic chemodosimeter immobilized on a solid support, which offers advantages in identifying the desired compounds in complex natural product mixtures. To isolate only compounds with the target functional groups, the click chemistry concept was adopted. The model system presented here was developed for natural products with a terminal alkyne. Using our newly designed alkyne sensing beads with the aforementioned features, we have readily identified, quantified, and isolated compounds with a terminal alkyne group from plant extracts.     

Conformational Parameters of the Sandalwood-Odor Activity: Conformational calculations on sandalwood odor

The conformational parameters responsible for sandalwood odor were investigated by the “active-analog approach”. The pharmacophoric (osmophoric) pattern of sandalwood-odor molecules can be outlined as three points: the OH group (point PI), a lipophilic group (point P2) 2.9–3.0 Å distant from the OH group, and a bulky rigid group (point P3), represented as a dummy atom in the middle of the alicyclic system (norbornane bicycle or cyclopentene ring) or a quaternary C-atom. This concept was tested on a series of representative sandalwood-odor compounds and on some structurally similar, but odorless substances.     

Palladium-catalyzed intramolecular α-arylation of aliphatic ketone, formyl, and nitro groups

Intramolecular arylation of properly designed substrates bearing a ketone, formyl, or nitro terminating group was achieved by use of a PdCl₂(Ph₃P)₂-Cs₂CO₃ reaction system to form a variety of carbocyclic compounds. Arylation in ketone compounds afforded benzene-annulated bridged or spirocycloalkanone derivatives, depending on the structure of the cyclization precursors. Arylation in formyl compounds occurred at the α-position (α-arylation) or at the carbonyl carbon (carbonyl-arylation) depending on the structure of the cyclization precursors and on the reaction solvent. An α-arylated secondary nitro group was partially transformed to ketone in the manner of the Nef reaction, whereas a tertiary nitro group was partially eliminated to afford a styrene-type olefin.     

Pharmacophore mapping and electronic feature analysis for a series of nitroaromatic compounds with antitubercular activity

A five point pharmacophore was generated using PHASE for a series of nitroaromatic compounds and their congeners as antitubercular agents. The generated pharmacophore yielded significant 3D‐QSAR model with r² of 0.890 for a training set of 92 molecules. The model also showed excellent predictive power with correlation coefficient Q² of 0.857 for a test set of 31 compounds. The pharmacophore indicated that presence of a nitro group, a piperazine moiety, one aromatic ring feature and two acceptor features are necessary for potent antitubercular activity. The pharmacophore was supported by electronic property analysis using density functional theory (DFT) at B3LYP/3–21*G level. Molecular electrostatic profile of the compounds was consistent with the generated pharmacophore model, particularly appearance of localized negative potential regions near both the oxygen atoms of nitro group extending laterally to the isoxazole ring system/amide bond in the most active compounds. Calculated data further revealed that all active compounds have smaller LUMO energies located over the nitro group, furan ring, and isoxazole ring/amide bond attached to it. Higher negative values of LUMO energies concentrated over the nitro group are indicative of the electron acceptor capacity of the compounds, suggesting that these compounds are prodrugs and must be activated by TB‐nitroreductase. The results obtained from this study should aid in efficient design and development of nitroaromatic compounds as antitubercular agents. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

17O and 13C nuclear magnetic resonance study of polyfluorinated carbonyl compounds

δ¹⁷O- and δ¹³C values are reported for 15 polyfluorinated carbonyl compounds. If the R_f group is separated from the carbonyl group by less than two carbon atoms a marked increase in the nuclear shielding of ¹³C(C=O) and a marked decrease in the nuclear shielding of the ¹⁷O(C=O) nucleus is observed. This is ascribed to the differing effects of the R_f group on the σ and the π system of the carbonyl unit. The effect on the σ-manifold leads to increase in shielding but it may be offset (as in the case of the ¹⁷O nucleus) by destabilization of the π system. UV spectroscopic data for some polyfluorinated carbonyl compounds support these arguments.     

QSAR and pharmacophore analysis on amides against drug-resistant S. aureus

Considering the worth of developing new antibacterial agents against drug-resistant Stapylococcus aureus, the present study explores the structure-activity relationships analysis of N-(2-hydroxy-4(or 5)-nitro/aminophenyl)benzamide and phenylacetamide derivatives using classical QSAR and 3D-common-feature pharmacophore hypothese approaches. QSAR analysis revealed that the compounds possessing a methylene group between the phenyl and the carboxyamido moiety played a role for decreasing the activity. On the other side, substituent effects on position R1 was found important for the activity and holding a substituent possessing a minimum width property on this position like as alkyl groups enhanced the activity. Moreover, substituting position R3 with a group enhancing the electron-donor capability of the phenolic ring system increased the potency. 3D-common-feature pharmacophore approach considered that the conformational properties of the compounds were important for the activity against drug-resistant S. aureus and compounds possessing a benzamide moiety rather than phenylacetamide structure increased the activity. Furthermore, holding NO2 and OH groups on the phenyl ring attached to the benzamide moiety was important for improving the potency against drug-resistant S. aureus.     

Diterpene lactones with labdane, halimane and clerodane frameworks

The labdane, halimane and clerodane type diterpenoids are compounds that have been isolated in plants of several families. These molecules and their derivatives with a lactone group on the side chain or on the decaline system, have a great interest because of their biological properties as insect antifeedant, antiviral, cytotoxic and trypanocidal. The scope of this review is lactones diterpenoids with labdane, halimane and clerodane frameworks.     

Molecular-level functionalization of electrode surfaces

An ultra-thin film of functional molecule(s) can be deposited on an electrode, which then serves as a device to amperometrically monitor compounds of biological interest. The methods of surface functionalization, mostly on tin oxide (SnO₂) electrodes, include: chemical modification (covalent bond formation between the surface OH group with a functional group of a molecule); the Langmuir-Blodgett technique, where the NH₂ group of a long-chain alkylamine is bound to an enzyme via a small dialdehyde molecule as spacer; and electropolymerization of pyrrole in an electrolyte containing a single enzyme or a sequentially operating bienzyme system. The results of such investigations by the author’s group are presented.     

Metalloid group 14 cluster compounds: an introduction and perspectives to this novel group of cluster compounds

Metalloid cluster compounds of group 14 of the general formulae E(n)R(m) with n > m (E = Si, Ge, Sn and Pb, tetrel elements; R = ligand), where "naked" tetrel atoms are present as well as ligand-bound tetrel atoms, represent a novel class of cluster compounds in group 14 chemistry. Since the "naked" tetrel atoms in these clusters exhibit an oxidation state of 0, the average oxidation state of the tetrel atoms in such metalloid group 14 cluster compounds is between 0 and 1. Thus, these cluster compounds may be seen as intermediates on the way to the elemental state. Therefore, interesting properties maybe expected for these compounds which might complement results from nanotechnology. During the last years many different syntheses of such novel cluster compounds have been introduced, leading to several metalloid group 14 cluster compounds which exhibit new and unusual structure and bonding properties. In this tutorial review an account is given of the first steps in this novel field of group 14 chemistry. Special attention is focused on structural features and bonding properties.     

The reaction of carbanions from 3-methyl-5-phenylisoxazole with electrophilic compounds

The reactivity of 3-methyl-5-phenylisoxazole against electrophilic compounds in the presence of different bases is studied. With n-BuLi, alkylated products at C-4 position and C-3 methyl group, and, in a few cases, dialkylated isoxazoles are obtained. When the reactions are carried out with LICA, the nature of the alkylated products depends on the alkyl halide used. By using LICA-TMEDA, as deprotonating system, regio-selective reaction at the C-3 methyl group is found.     

氟碳磷脂的合成及其脂质体的生成

合成了两种具有氟碳疏水性链的磷脂, 其极性部分分别为胆碱和磷酸根. 超声分散下, 上述两种磷脂均可形成腈质体, 以电子显微镜观察和动态光散射测定得到胆碱形成的脂质体的尺寸在32-37nm左右. 而对后者的光散射测定得出的尺寸较大并与溶液的pH值有关. 具有胆极性基的氟碳脂质体如同相应的碳氢磷脂一样, 具有包容水溶性受物的能力,但透光性更好. 从荧光探针的荧光强度对温度变化的研究指出, 在53℃左右胆碱型氟碳脂质体发生了相变.     

Synthesis and antitumor activity of benzimidazolyl-1,3,5-triazine and benzimidazolylpyrimidine derivatives

Triamino-substituted 1,3,5-triazine and pyrimidine derivatives were synthesized and tested for antitumor activities using some human cancer cell lines and murine leukemia cell lines. All the compounds having benzimidazolyl and morpholino groups as substituents on the 1,3,5-triazine ring showed antitumor activity. Pyrimidine derivatives having the same groups as substituents also showed antitumor activity. Among them, the compounds having 1-benzimidazolyl, morpholino and cis-2,3-dimethylmorpholino groups as substituents on the 1,3,5-triazine ring or pyrimidine ring exhibited the most potent antitumor activity, and these compounds exhibited no or very weak aromatase inhibitory activity. In contrast, the compounds having imidazolyl group instead of benzimidazolyl group as a substituent on the 1,3,5-triazine ring showed a potent aromatase inhibitory activity.     

Separation and identification of illicit heroin samples by liquid chromatography using an alumina and C18 coupled column system and photodiode array detection

The analysis of illicit heroin and opium samples on a coupled alumina and C18 column system is described. The compounds to be analysed can be divided into two groups: those with low pKa values, such as caffeine, papaverine and noscapine, and those with high pKa values, such as heroin, acetylcodeine, O6-monoacetylmorphine, procaine, codeine, morphine and strychnine. The first group can best be separated on a C18 column, whereas alumina is more suitable for the second group. Previously reported criteria for choosing proper buffer systems for ion-exchange separations on alumina were used together with an iterative regressive optimization procedure developed in our laboratory. The system can be used with and without valve-switching, depending on the sample type. The peak purity of the judicially important components heroin and O6-monoacetylmorphine has been checked with a photodiode array detector and by use of advanced software.     

Approaches to the Synthesis of Gibberellic Acid. Construction of the B,C and D Ring System

One of the most challenging aspects of the synthesis of gibberellic acid² and structurally related compounds such as steviol³ is the construction of the bicyclo[3.2.1]octane system with the unusual features of an exocyclic methylene group adjacent to a bridgehead tertiary hydroxyl group. In gibberellic acid this structural feature comprises the C, D ring system, which is fused to the five-membered B ring.