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61.
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63.
Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions
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Ing. Martin Holan Dr. Radek Pohl Dr. Ivana Císařová Dr. Blanka Klepetářová Prof. Dr. Peter G. Jones Dr. Ullrich Jahn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9877-9888
Densely functionalized cyclopentane derivatives with up to four consecutive stereocenters are assembled by a tandem Michael addition/single‐electron transfer oxidation/radical cyclization/oxygenation strategy mediated by ferrocenium hexafluorophosphate, a recyclable, less toxic single‐electron transfer oxidant. Ester enolates were coupled with α‐benzylidene and α‐alkylidene β‐dicarbonyl compounds with switchable diastereoselectivity. This pivotal steering element subsequently controls the diastereoselectivity of the radical cyclization step. The substitution pattern of the radical cyclization acceptor enables a switch of the cyclization mode from a 5‐exo pattern for terminally substituted olefin units to a 6‐endo mode for internally substituted acceptors. The oxidative anionic/radical strategy also allows efficient termination by oxygenation with the free radical 2,2,6,6‐tetramethyl‐1‐piperidinoxyl, and two C?C bonds and one C?O bond are thus formed in the sequence. A stereochemical model is proposed that accounts for all of the experimental results and allows the prediction of the stereochemical outcome. Further transformations of the synthesized cyclopentanes are reported. 相似文献
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Radek Liboska 《Tetrahedron letters》2008,49(39):5629-5631
We present herein a straightforward synthesis of N-Fmoc-protected synthons derived from a phosphinic analogue of methionine. These precursors were used successfully for the solid-phase synthesis of methionine-mimic phosphinopeptides using BOP-catalyzed coupling without protection of the phosphoryl moiety. We also prepared a new type of pseudopeptide derived from a phosphinic analogue of norleucine with a -PO(OH)-CH2-COOR moiety. 相似文献
66.
Sachl R Stepánek M Procházka K Humpolícková J Hof M 《Langmuir : the ACS journal of surfaces and colloids》2008,24(1):288-295
Steady-state and time-resolved fluorescence measurements were used to study the relaxation of the microenvironment of hydrophobic probes 6-propionyl-2-(dimethylamino)naphthalene (prodan) and 6-dodecanoyl-2-(dimethylamino)naphthalene (laurdan) in systems containing vesicles formed by the amphiphilic diblock copolymer poly(epsilon-caprolactone)-block-poly(ethylene oxide) (PCL-PEO) and water/tetrahydrofurane (THF) solvent mixtures. It was found that in case of prodan, both steady-state and time-resolved emission spectra were composed of two subspectra corresponding to the emission of prodan molecules located (i) in fairly rigid (effectively viscous) and hydrophobic domains of the vesicles close to the PCL/PEO interface and (ii) in a more polar and less viscous medium (in the bulk solution). The fraction of the emission from the more polar microenvironment increases with increasing content of THF in the system. Laurdan, in contrast to prodan, appeared to be solubilized preferentially in the hydrophobic domains up to 30 vol % of THF content, and its emission spectra changed only due to swelling of hydrophobic PCL domains by added THF. The study shows that the analysis of the time-resolved emission from a probe distributed in two media is, in principle, possible, but it is quite complex and appreciably less accurate, and the relaxation times are ill-defined averages of several processes. The bimodal or shoulder-containing time-resolved spectra have to be decomposed in pertinent time-resolved subspectra and treated separately. Another important result of the study is a piece of knowledge concerning the motion of the probe with respect to the vesicle. In the studied complex system, not only the relaxation of the solvent and reorganization of polymer segments around the fluorescent headgroup of the probe affect the emission but also a lateral motion of the probe with respect to the nanoparticle within the lifetime of the excited state contributes significantly to the relaxation and to the relatively slow time-resolved Stokes shift. 相似文献
67.
Tousek J Van Miert S Pieters L Van Baelen G Hostyn S Maes BU Lemière G Dommisse R Marek R 《Magnetic resonance in chemistry : MRC》2008,46(1):42-51
Indoloquinoline alkaloids represent an important class of antimalarial, antibacterial and antiviral compounds. They have been shown to bind to DNA via intercalation preferentially at GC-rich sequences containing nonalternating CC sites. The stability of complexes formed with biological macromolecules depends on noncovalent binding. In the present study, the ability of indoloquinolines to form intermolecular interactions with solvents was investigated by using NMR spectroscopy and density functional theory (DFT) (B3LYP/6-31G**) calculations. NMR data measured for indoloquinoline bases and the corresponding hydrochlorides are discussed in relation to the structure. DFT calculations of shielding constants in vacuo and in solution allowed the investigation of the influence of the environment on the NMR parameters. Calculations incorporating solvent effects indicated significant changes in the anisotropy of the electron distribution, reflected in the span of the chemical shielding tensor (Omega = sigma11 - sigma33). Solvent effects on the span of the 13C and 15N shielding tensor depended on the type of atom and the data indicated a significant influence of solute-solvent interactions. 相似文献
68.
Tsikouris O Bartl T Tousek J Lougiakis N Tite T Marakos P Pouli N Mikros E Marek R 《Magnetic resonance in chemistry : MRC》2008,46(7):643-649
Substituted pyrazolopyridines are potent inhibitors of phosphodiesterases and cyclin-dependent kinases. In this study, NMR was used to investigate the potential N1-H and N2-H tautomerism of 5-substituted pyrazolo[3,4-c]pyridine derivatives. Six compounds were fully characterized by using (1)H, (13)C, and (15)N chemical shifts and indirect (1)H--(13)C and (1)H--(15)N coupling constants. The (1)H NMR spectra were measured over a broad range of temperatures. All of the compounds were shown to exist predominantly in the N1-H tautomeric form. Complementary quantum-chemical calculations of the chemical shieldings and indirect spin-spin couplings support the structural conclusions drawn. 相似文献
69.
Bhaskar Sharma Y. Indra Neela G. Narahari Sastry 《Journal of computational chemistry》2016,37(11):992-1004
Quantum chemical calculations have been performed at CCSD(T)/def2‐TZVP level to investigate the strength and nature of interactions of ammonia (NH3), water (H2O), and benzene (C6H6) with various metal ions and validated with the available experimental results. For all the considered metal ions, a preference for C6H6 is observed for dicationic ions whereas the monocationic ions prefer to bind with NH3. Density Functional Theory–Symmetry Adapted Perturbation Theory (DFT‐SAPT) analysis has been employed at PBE0AC/def2‐TZVP level on these complexes (closed shell), to understand the various energy terms contributing to binding energy (BE). The DFT‐SAPT result shows that for the metal ion complexes with H2O electrostatic component is the major contributor to the BE whereas, for C6H6 complexes polarization component is dominant, except in the case of alkali metal ion complexes. However, in case of NH3 complexes, electrostatic component is dominant for s‐block metal ions, whereas, for the d and p‐block metal ion complexes both electrostatic and polarization components are important. The geometry (M+–N and M+–O distance for NH3 and H2O complexes respectively, and cation–π distance for C6H6 complexes) for the alkali and alkaline earth metal ion complexes increases down the group. Natural population analysis performed on NH3, H2O, and C6H6 complexes shows that the charge transfer to metal ions is higher in case of C6H6 complexes. © 2016 Wiley Periodicals, Inc. 相似文献
70.
Back Cover: GM1 Ganglioside Inhibits β‐Amyloid Oligomerization Induced by Sphingomyelin (Angew. Chem. Int. Ed. 32/2016)
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