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141.
142.
[reaction: see text] The total synthesis of the novel metabolite pyridovericin 1 is reported. The synthesis of this key intermediate in our proposed biomimetic synthesis of pyridomacrolidin 2 has been accomplished in good yield from readily available 2,4-dihydroxypyridine.  相似文献   
143.
The Wittig reaction of butylidenetriphenylphosphorane with benzaldehyde using LiHMDS as base in THF was studied. The stereochemical drift (different ratio obtained in alkenes versus oxaphosphetane intermediates) was followed by low-temperature 1D NMR techniques. A retro-Wittig reaction is demonstrated using 13C and 31P saturation transfer experiments and homonuclear DPFGSE-ROE techniques.  相似文献   
144.
A set of tris(2-ureidobenzyl)amines 3 was prepared and their dimerization processes thoroughly investigated. In spite of their inherent flexibility, tris(ureas) 3 form dimeric aggregates both in the solid state and in solution. Evidence for the existence of these dimeric species was provided by a combination of techniques (X-ray analysis, NMR and IR spectroscopy, and ESI-MS). The association constants and thermodynamic parameters for the dimerization processes of selected tris(ureas) were determined and show that they are enthalpically driven. Heterodimerization experiments in solution reveal a high degree of self-recognition or narcissistic self-sorting. On the other hand, desymmetrized tris(ureas) derived from 3 self-assemble with modest regioselectivities depending on the terminal substituent of every urea functionality.  相似文献   
145.
The dinuclear phenolato-bridged complex [(mL)Mn(II)Mn(II)(mL)](ClO(4))(2) (1(ClO(4))(2)) has been obtained with the new [N(4)O] pentadentate ligand mL(-) (mLH=N,N'-bis-(2-pyridylmethyl)-N-(2-hydroxybenzyl)-N'-methyl-ethane-1,2-diamine) and has been characterised by X-ray crystallography. X- and Q-band EPR spectra were recorded and their variation with temperature was examined. All spectra exhibit features extending over 0-800 mT at the X band and over 100-1450 mT at the Q band, features that are usually observed for dinuclear Mn(II) complexes. Cyclic voltammetry of 1 exhibits two irreversible oxidation waves at E(1)(p)=0.89 V and E(2)(p)=1.02 V, accompanied on the reverse scan by an ill-defined cathodic wave at E(1')(p)=0.56 V (all measured versus the saturated calomel electrode (SCE)). Upon chemical oxidation with tBuOOH (10 equiv) at 20 degrees C, 1 is transformed into the mono-mu-oxo species [(mL)Mn(III)-(mu-O)-Mn(III)(mL)](2+) (2), which eventually partially evolves into the di-mu-oxo species [(mL)Mn(III)-(mu-O)(2)-Mn(IV)(mL)](n+) (3) in which one of the aromatic rings of the ligand is decoordinated. The UV/Vis spectrum of 2 displays a large absorption band at 507 nm, which is attributed to a phenolate-->Mn(III) charge-transfer transition. The cyclovoltammogram of 2 exhibits two reversible oxidation waves, at 0.65 and 1.16 V versus the SCE, corresponding to the Mn(III)Mn(III)/Mn(III)Mn(IV) and Mn(III)Mn(IV)/Mn(IV)Mn(IV) oxidation processes, respectively. The one-electron electrochemical oxidation of 2 leads to the mono-mu-oxo mixed-valent species [(mL)Mn(III)-(mu-O)-Mn(IV)(mL)](3+) (2 ox). The UV/Vis spectrum of 2 ox exhibits one large band at 643 nm, which is attributed to the phenolate-->Mn(IV) charge-transfer transition. 2 ox can also be obtained by the direct electrochemical oxidation of 1 in the presence of an external base. The 2 ox and 3 species exhibit a 16-line EPR signal with first peak to last trough widths of 125 and 111 mT, respectively. Both spectra have been simulated by using colinear rhombic Mn-hyperfine tensors. Mechanisms for the chemical formation of 2 and the electrochemical oxidation of 1 into 2 ox are proposed.  相似文献   
146.
Metal-mediated self-assembly is emerging as a very important strategy for the synthesis of supramolecular species. Still, a major challenge in coordination supramolecular chemistry continues to be the characterization of the self-assembled complexes and the investigation of their dynamic behaviour in solution. In this context, NMR spectroscopy appears as a unique and powerful methodology. This practical-oriented review describes the rich variety of NMR techniques which are applied to the investigation of different aspects of the structure and behaviour of supramolecular complexes. “Classic” 1D NMR spectra reflect characteristic chemical shifts due to metal–ligand interactions or encapsulation phenomena, as well as symmetry and chiral properties of host–guest assemblies. Mainstream 1H, 13C, 19F and 31P spectra are eventually complemented by the use of NMR-active metal nuclides. Homo- and heteronuclear 2D correlation experiments are ubiquitous in the literature, providing through-bond and through-space connectivities. Increasingly, diffusion measurements are also gaining popularity in this field, being used to gain information about molecular size, intermolecular interactions and even association constants of supramolecular complexes. Knowledge about the thermodynamic properties and the dynamic behaviour of coordination supramolecular assemblies is essential for the development of their practical applications. The most frequently used NMR methodologies for the calculation of association constants (simple signal integration, NMR titration and diffusion measurements) and for the investigation of dynamic supramolecular equilibria (lineshape analysis, selective inversion recovery experiments and 2D EXSY spectra) are described, together with the use of variable-temperature investigations for the determination of the thermodynamic and activation parameters of self-assembly and encapsulation processes.  相似文献   
147.
To mimic the carboxylate-rich active site of the manganese catalases more closely we introduced carboxylate groups into dimanganese complexes in place of nitrogen ligands. The series of dimanganese(III,IV) complexes of tripodal ligands [Mn(2)(L)(2)(O)(2)](3+/+/-/3-) was extended from those of tpa (1) and H(bpg) (2) to those of H(2)(pda) (3) and H(3)(nta) (4) (tpa=tris-picolylamine, H(bpg)=bis-picolylglycylamine, H(2)(pda)=picolyldiglycylamine, H(3)(nta)=nitrilotriacetic acid). While 3 [Mn(2)(pda)(2)(O)(2)][Na(H(2)O)(3)] could be synthesized at -20 degrees C and characterized in the solid state, 4 [Mn(2)(nta)(2)(O)(2)](3-) could be obtained and studied only in solution at -60 degrees C. A new synthetic procedure for the dimanganese(III,III) complexes was devised, using stoichiometric reduction of the dimanganese(III,IV) precursor by the benzil radical with EPR monitoring. This enabled the preparation of the parent dimanganese(III,III) complex 5 [Mn(2)(tpa)(2)(O)(2)](ClO(4))(2), which was structurally characterized. The UV/visible, IR, EPR, magnetic, and electrochemical properties of complexes 1-3 and 5 were analyzed to assess the electronic changes brought about by the carboxylate replacement of pyridine ligands. The kinetics of the oxo ligand exchanges with labeled water was examined in acetonitrile solution. A dramatic effect of the number of carboxylates was evidenced. Interestingly, the influence of the second carboxylate substitution differs from that of the first one probably because this substitution occurs on an out-of-plane coordination while the former occurs in the plane of the [Mn(2)O(2)] core. Indeed, on going from 1 to 3 the exchange rate was increased by a factor of 50. Addition of triethylamine caused a rate increase for 1, but not for 3. The abilities of 1-3 to disproportionate H(2)O(2) were assessed volumetrically. The disproportionation exhibited a sensitivity corresponding to the carboxylate substitution. These observations strongly suggest that the carboxylate ligands in 2 and 3 act as internal bases.  相似文献   
148.
The hetero-Diels-Alder reactions of 4-alkenylthiazoles with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) lead to new heteropolycyclic systems in excellent yields and high levels of stereocontrol through an exclusively suprafacial approach. 4-Alkenylthiazoles with a stereogenic center placed at the alkenylic substituent react with PTAD giving the corresponding chiral cycloadducts in moderate diastereomeric excesses. The stereochemical course is dominated by the steric interactions at the two diastereomeric transition states. A computational study of these processes with structurally simpler reagents has been carried out. A concerted pathway via a highly asynchronous transition state is preferred for 2-unsubstituted 4-vinyl and 4-styrylthiazoles. However, two alternative and equally likely pathways, concerted and stepwise, have been found to be followed by 2-methyl- or 2-phenyl-substituted 4-styrylthiazoles. The concerted pathway features a highly asynchronous transition state. For the stepwise pathway, the rate-determining step is the first one, as the energy barrier for the second step is virtually nonexistent.  相似文献   
149.
Gene-directed enzyme prodrug therapy (GDEPT) has been intensively studied as a promising new strategy of prodrug delivery, with its main advantages being represented by an enhanced efficacy and a reduced off-target toxicity of the active drug. In recent years, numerous therapeutic systems based on GDEPT strategy have entered clinical trials. In order to deliver the desired gene at a specific site of action, this therapeutic approach uses vectors divided in two major categories, viral vectors and non-viral vectors, with the latter being represented by chemical delivery agents. There is considerable interest in the development of non-viral vectors due to their decreased immunogenicity, higher specificity, ease of synthesis and greater flexibility for subsequent modulations. Dendrimers used as delivery vehicles offer many advantages, such as: nanoscale size, precise molecular weight, increased solubility, high load capacity, high bioavailability and low immunogenicity. The aim of the present work was to provide a comprehensive overview of the recent advances regarding the use of dendrimers as non-viral carriers in the GDEPT therapy.  相似文献   
150.
The effect of Antipyrin upon the antioxidant activity of the riboflavin has been evidenced using chemiluminescent system luminol–hydrogen peroxide, in Tris–HCl buffer, pH 8.5. It was found that riboflavin antioxidant activity depends on the reaction time and the Antipyrin concentration. Using ESR spectroscopy the hydroxyl radical generation, in the mentioned chemiluminescent system, was evidenced. The interaction between reactants was also investigated by UV-VIS and fluorescence spectroscopy. The effect of Antipyrin concentration upon the riboflavin fluorescence has also been investigated. The fluorescence quenching by Antipyrin is not significant and subsequently the riboflavin fluorescence quenching doesn’t indicate an electron transfer process through diffusion-controlled mechanism. The results are discussed with relevance to the redox processes of riboflavin.  相似文献   
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