Polyoxime-urethanes have been synthesized from dioximes and diisocyanates, and their structures have been ascertained by elemental analysis and infrared spectroscopy. They can be represented by the general formula: These polymer films were photolyzed by using a high-pressure 100-W mercury lamp, and the rate of decomposition of the N? O bond was determined by use of ultraviolet and infrared spectra, or comparing the photochemical behavior with that of corresponding model compounds. Upon irradiating these polymers in the presence or absence of sensitizers or a hydrogen donor, there were obtained photolyzed polymers of low molecular weight, of which the molecular weights were estimated by observing the viscosity changes. To deduce the mechanism of photodegradation of polyoxime-urethane, photolysis of benzophenone oxime-phenyl urethane was investigated as a model compound. 相似文献
The systematic oxidation reactions of a wide range of alcohols have been carried out by using an iron porphyrin complex in order to understand their relation to cytochrome P-450 enzymes and to have a practical application to organic synthesis. The iron porphyrin complex catalyzed efficiently alcohol oxidation to the respective carbonyl compound via a high-valent iron-oxo porphyrin intermediate ((Porp)Fe=O+). Several mechanistic studies such as isotope 18O labeling, deuterium isotope effect, linear free energy relationship, and ring-opening of radical clock substrate, have suggested that the alcohol is oxidized by a sequence of reactions involving an alpha-hydroxyalkyl radical intermediate and oxygen rebound to form the gem-diol, dehydration of which yields the carbonyl compounds. Moreover, it has been proposed that a two-state reactivity mechanism can also be adopted for alcohol oxidation reactions in iron porphyrin model systems as exhibited by P-450 enzymes. 相似文献
A new and regioselective [4+2] benzannulation protocol toward polysubstituted benzenes was developed. A nitroalkane derivative, which was prepared from Baylis-Hillman adduct, served as the four-carbon unit and a Michael acceptor as a two-carbon unit. Vinyltriphenylphosphonium salt could also be used as a Michael acceptor efficiently. 相似文献
The structure of the title compound, C15H27N2+·ClO4?, consists of a monoprotonated sparteinium cation and a perchlorate anion. The two tertiary N atoms of the cation, one perchlorate O atom and a H atom form a bifurcated hydrogen bond, the four hydrogen‐bonding atoms being nearly in the same plane. 相似文献
The effect of thioamide substitution on the conformational stability of an azaglycine-containing peptide, For-AzaGly-NH2 (1), was investigated for the sake of finding possible applications by using ab initio and DFT methods. As model compounds, For-[psiCSNH]-AzaGly-NH2 (2), For-AzaGly-[psiCSNH]-NH2 (3), and For-[psiCSNH]-AzaGly-[psiCSNH]-NH2 (4) were used. Two-dimensional phi-psi potential energy surfaces (PESs) for 2-4 were calculated at the B3LYP/6-31G*//HF/6-31G* level in gas (epsilon = 1.0) and in water (epsilon = 78.4) by applying the isodensity polarizable continuum model (IPCM) method. On the basis of these PESs, the minimum energy conformations for 2-4 were characterized at the B3LYP level with 6-31G*, 6-311G**, and 6-31+G** basis sets. The remarkable structural effect of thioamide substitution for 2-4 is that beta-strand structure is observed as a global or local minimum. The minima of 2-4 are also compared with those for glycine and thioamide-containing glycine peptides. Our theoretical results demonstrate that compounds 2-4 would be used to design controllable secondary structures. 相似文献
(+)-Monomorine has been synthesized under mild hydrogenation conditions initiating deprotection followed by intramolecular, sequential reductive amination reactions. The precursors could be prepared concisely using B-alkyl Suzuki cross coupling of a chiral homoallylamine and a vinyl iodide or an iodofuran derivative. 相似文献
Daptomycin is a cyclic anionic lipopeptide antibiotic recently approved for the treatment of complicated skin infections (Cubicin). Its function is dependent on calcium (as Ca2+). Circular dichroism spectroscopy indicated that daptomycin experienced two structural transitions: a transition upon interaction of daptomycin with Ca2+, and a further transition upon interaction with Ca2+ and the bacterial acidic phospholipid, phosphatidyl glycerol. The Ca2+-dependent insertion of daptomycin into model membranes promoted mild and more pronounced perturbations as assessed by the increase of lipid flip-flop and membrane leakage, respectively. The NMR structure of daptomycin indicated that Ca2+ induced a conformational change in daptomycin that increased its amphipathicity. These results are consistent with the hypothesis that the association of Ca2+ with daptomycin permits it to interact with bacterial membranes with effects that are similar to those of the cationic antimicrobial peptides. 相似文献
A new trihydroxy briarane-related diterpenoid, junceellolide I (1), along with a known metabolite, (1R,2R,5Z,7R,8S,9R,10R,12R,14R,17S)-2,14-diacetoxy-8,17-epoxy-9,12-dihydroxybriara-5,11(20)-dien-19-one (2), have been isolated from the gorgonian coral Junceella fragilis, collected off the southern Taiwan coast. The structure, including the relative configuration of the new compound 1, was elucidated by the combination of spectral data, particularly in high-resolution 1H- and 13C-NMR spectroscopy utilizing COSY, HMBC, HMQC, and NOESY experiments. 相似文献