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561.
A facile synthesis of imidazo[4,5-b]pyridines and -pyrazines is described using a Pd-catalyzed amide coupling reaction. This reaction provides quick access to products with substitution at N1 and C2. A model system relevant to the natural product pentosidine has been demonstrated, as well as the total synthesis of the mutagen 1-Me-5-PhIP. 相似文献
562.
In the course of our studies of nucleophilic attack on electronically unsaturated benzoheterocycle triosmium clusters we have studied the reaction of the 2-methylbenzoxazole complex (μ-H)Os3(CO)9(μ3-η2-2-CH3–C7H3NO) (1) with hydride followed by protonation with acid. In sharp contrast to our previous studies with related benzoheterocycle triosmium clusters, where the nature of the heterocycle controls the regiochemistry of nucleophilic attack, we observe here an unusual ring opening of the heterocyclic ring, coupled with rearrangement of the carbocyclic ring to a 2-imino-ethyl-phenol complex (μ-H)Os3(CO)9(μ3-η3-N=CHCH3–C6H3(OH)) (2). Deuterium labeling experiments verify initial attack by hydride at the 2-position followed by protonation at oxygen. Reaction of 1 with two equivalents of hydride followed by two equivalents of acid results in reduction of the C=N bond in 2 and on standing in air, oxidation of the carbocyclic ring occurs to give the 2-ethyl-amino hydroquinolyl derivative (μ-H)Os3(CO)9(μ3-η3-NHCH2CH3–C6H3(2-O)(5-OH)) (3). The solid-state structure of 3 is reported and a plausible mechanism, supported by deuterium labeling experiments, is presented, for the formation of 2 and 3. 相似文献
563.
Dahlstrand C Rosenberg M Kilså K Ottosson H 《The journal of physical chemistry. A》2012,116(20):5008-5017
The singlet ground states and lowest triplet states of penta- and heptafulvene, their benzannulated derivatives, as well as the lowest quintet states of pentaheptafulvalenes, either the parent compound or compounds in which the two rings are intercepted by either an alkynyl or a phenyl segment, were investigated at the (U)OLYP/6-311G(d,p) density functional theory level. The influence of (anti)aromaticity was analyzed by the structure-based aromaticity index HOMA, the harmonic oscillator model of aromaticity. The extent of (anti)aromatic character was also evaluated in terms of the π-electron (de)localization as measured by the π component of the electron localization function (ELF(π)). The natural atomic orbital (NAO) occupancies were calculated in order to evaluate the degree of π-electron shift caused by the opposing electron-counting rules for aromaticity in the electronic ground state (S(0); Hückel's rule) and the first ππ* excited triplet state (T(1); Baird's rule). Pentaheptafulvalene (5) shows a shift of 0.5 π electrons from the 5-ring to the 7-ring when going from the S(0) state to the lowest quintet state (Qu(1)). The pentaheptafulvalene 5 and [5.6.7]quinarene 7 were also investigated in their 90° twisted conformations. From our study it is apparent that excitation localization in fulvalenes, but not in fulvenes, to a substantial degree is determined by aromaticity localization to triplet biradical 4n π-electron cycles. Isolated benzene rings in these compounds tend to remain as closed-shell 6π-electron cycles. 相似文献
564.
Knoll W Kaneno D Bobek MM Brecker L Rosenberg MG Tomoda S Brinker UH 《The Journal of organic chemistry》2012,77(3):1340-1360
A study of adamantanylidenes having a γ-substituent (R) was undertaken to gauge how inductive and steric effects of remotely positioned functional groups influence intra- and intermolecular product selectivity. 3H-Diazirines were thermolyzed or photolyzed to generate the corresponding carbenes. On rapid heating, the resulting carbenes isomerized to 2,4-didehydroadamantanes by intramolecular 1,3-CH insertions. When R was an electron donor (R(D)) mostly asymmetric 1-substituted derivatives were produced but when it was an electron acceptor (R(A)) the symmetric 7-substituted ones were formed. When solutions were exposed to UV-A light, intermolecular adducts from the carbenes and solvent predominated with lesser amounts of intramolecular product being formed. Valence isomerization of 3H-diazirines also afforded diazo compounds. In methanol, protonation of diazo compounds to give the corresponding 2-adamantyl cations exceeds their coupling. This diversion was controlled with fumaronitrile by trapping the diazo compounds. The adducts possessed mostly anti configurations with R = R(D) and syn arrangements with R = R(A). The connection between as- and anti-product formation and that of s- and syn-products was deemed to be the consequence of a rapid equilibrium between two distinct carbene conformations. This was qualified and quantified using ab initio calculations and NBO analyses. 相似文献
565.
Back BB Baker MD Ballintijn M Barton DS Betts RR Bickley AA Bindel R Budzanowski A Busza W Carroll A Chai Z Decowski MP García E Gburek T George N Gulbrandsen K Gushue S Halliwell C Hamblen J Hauer M Heintzelman GA Henderson C Hofman DJ Hollis RS Hołyński R Holzman B Iordanova A Johnson E Kane JL Katzy J Khan N Kucewicz W Kulinich P Kuo CM Lin WT Manly S McLeod D Mignerey AC Nouicer R Olszewski A Pak R Park IC Pernegger H Reed C Remsberg LP Reuter M Roland C Roland G Rosenberg L Sagerer J 《Physical review letters》2006,97(1):012301
We report on measurements of directed flow as a function of pseudorapidity in Au + Au collisions at energies of square root of SNN = 19.6, 62.4, 130 and 200 GeV as measured by the PHOBOS detector at the BNL Relativistic Heavy Ion Collider. These results are particularly valuable because of the extensive, continuous pseudorapidity coverage of the PHOBOS detector. There is no significant indication of structure near midrapidity and the data surprisingly exhibit extended longitudinal scaling similar to that seen for elliptic flow and charged particle pseudorapidity density. 相似文献
566.
Beckmann PA Rosenberg J Nordstrom K Mallory CW Mallory FB 《The journal of physical chemistry. A》2006,110(11):3947-3953
We have observed and modeled the 1H and 19F solid-state nuclear spin relaxation process in polycrystalline 3-(trifluoromethyl)phenanthrene. The relaxation rates for the two spin species were observed from 85 to 300 K at the low NMR frequencies of omega/2pi = 22.5 and 53.0 MHz where CF3 rotation, characterized by a mean time tau between hops, is the only motion on the NMR time scale. All motional time scales (omegatau < 1, omegatau approximately 1, and omegatau > 1) are observed. The 1H spins are immobile on the NMR time scale but are coupled to the 19F spins via the unlike-spin dipole-dipole interaction. The temperature dependence of the observed relaxation rates (the relaxation is biexponential) shows considerable structure and a thorough analysis of Bloch-Wangsness-Redfield theory for this coupled spin system is provided. The activation energy for CF3 rotation is 11.5 +/- 0.7 kJ/mol, in excellent agreement with the calculation in a 13-molecule cluster provided in the companion paper where the crystal structure is reported and detailed ab initio electronic structure calculations are performed [Wang, X.; Mallory F. B.; Mallory, C. W; Beckmann, P. A.; Rheingold, A. L.; Francl, M. M J. Phys. Chem. A 2006, 110, 3954]. 相似文献
567.
The density functional theory method has been applied to gain insights into the regioselectivity of nucleophilic attack and protonation of electron-deficient benzoheterocycle triosmium clusters. We report our computational results on the reaction of the green 46-electron triosmium clusters Os3(CO)(9)(mu3-eta2-(LH))(mu-H) (L = benzoxazole, 1a; benzothiazole, 1b; dihydroquinoline, 1c; 1,3-dehydroindoline, 1d; 4H-3,1-benzoxazine, 1e) with hydride (H-) and proton (H+) in order to elucidate factors affecting the observed differences in the structure of the kinetic products of these reactions. Transition-state calculations for the interconversion of the anionic tautomers resulting from H- attack on the clusters 1a-e show that the activation energies of these anionic clusters are considerably lower than the previously reported barriers for related neutral clusters. Calculations also reveal that the structures of the kinetic products resulting from sequential H-/H+ attack are determined by the protonation process. 相似文献
568.
Hana Vaisocherová Jan Snášel Tomáš Špringer Hana Šípová Ivan Rosenberg Josef Štěpánek Jiří Homola 《Analytical and bioanalytical chemistry》2009,393(4):1165-1172
Understanding the molecular mechanism of HIV-1 integrase (IN) activity is critical to find functional inhibitors for an effective
AIDS therapy. A robust, fast, and sensitive method for studying IN activity is required. In this work, an assay for real-time
label-free monitoring of the IN activity based on surface plasmon resonance was developed. This assay enabled direct monitoring
of the integration of a viral doubled-stranded (ds) DNA into the host genome. The strand transfer reaction was detected by
using two different DNA targets: supercoiled plasmid (pUC 19) and short palindrome oligonucleotide. The effect of the length
of the DNA target on the possibility to monitor the actual process of the strand transfer reaction is discussed. The surface
density of integrated ds-DNA was determined. IN binding to the oligonucleotide complexes and model DNA triplexes in the presence
of various divalent ions as metal cofactors was investigated as well. The assay developed can serve as an important analytical
tool to search for potential strand transfer reaction inhibitors as well as for the study of compounds interfering with the
binding of ds long terminal repeats–IN complexes with the host DNA.
HIV-1 integrase strand transfer activity was monitored in real time using a multichannel surface plasmon resonance biosensor.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
569.
B. A. Rosenberg 《Macromolecular Symposia》1987,7(1):17-26
A review of new results concerning kinetics, thermodynamics and mechanism of epoxy oligomers curing with various nucleophilic agents (amines, phenols, carboxylic acids) has been made. The concept of the mechanism of such reactions is formulated on the basis of this study. Kinetic data obtained are interpreted within the framework of cyclic transition state. The addition of nucleophilic agent to epoxy ring is rather complicated. It results from preliminary formation of homo- and heteroassociates of reaction system components which finally form reactive cyclic heteroassociates. Reaction products are formed as a result of monomolecular rearrangement with synchronous transfer of electrons in the reactive cyclic heteroassociates. 相似文献
570.