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71.
García Ruano JL Fraile A González G Martín MR Clemente FR Gordillo R 《The Journal of organic chemistry》2003,68(17):6522-6534
The addition of diazomethane and diazoethane to (5S,SS)- and (5R,SS)-5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones (1a and 1b) and their 4-methylderivatives (2a and 2b) proceeded in almost quantitative yields and complete regioselectivity. The observed pi-facial selectivity is determined by the configurations at both C-5 and the sulfinyl group, the later being the most important. The syn adducts were almost exclusively obtained from 1a and 2a in apolar solvents but the pi-facial selectivity was strongly decreased in more polar solvents. On the other hand, the major adducts from 1b and 2b were the anti ones and such predominance was slightly increased with solvent polarity. The exo-selectivity was complete in all the cases except for the anti approach to compounds 2a (in polar solvents) and 2b. The role of the sulfinyl group in this behavior was inferred by comparison of these results with those obtained in reactions of diazoalkanes with 5-methoxyfuran-2(5H)-one (3). Steric interactions seem to be the main ones responsible for the observed exo selectivity of reactions with diazoethane, but electronic factors, which can be modulated by the solvent, are also significant in the pi-facial selectivity control. DFT computational methods are able to correctly predict the reactivity, regioselectivity, and pi-facial selectivity exhibited by 5-alkoxyfuranones as well as their changes with the solvent polarity. A C-H.O hydrogen bond, involving the oxygen atom of the 5-alkoxy group at dipolarophiles and the endo-hydrogen atom at dipoles, seems to play a key role in the electronic interactions influencing the stereochemical course of these reactions. 相似文献
72.
Bianchini C Giambastiani G Laschi F Mariani P Vacca A Vizza F Zanello P 《Organic & biomolecular chemistry》2003,1(5):879-886
A new potentially hexadentate tetraazamacrocycle based on the cyclen skeleton has been synthesized and fully characterized. The macrocycle 4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-bis(methanephosphonic acid monoethyl ester) dipotassium salt (Me2DO2PME) contains mutually trans monoethyl ester phosphonate acid substituents on two nitrogen atoms, and trans methyl substituents on the other two nitrogen atoms. The protonation constants of this macrocycle and the stability constants of its complexes with Cu2+, Zn2+, Gd3+ and Ca2+ ions have been determined by pH potentiometric titrations. The protonation sequence of the macrocycle has been studied by 1H, 31P[1H] and 13C[1H] NMR spectroscopy: the first and second protonation steps take place at the methyl-substituted nitrogen atoms, while the third protonation involves one oxygen from a phosphonate group. Upon protonation, all the CH2 ring protons become magnetically inequivalent on the NMR time scale due to a slow conformational rearrangement, most likely occasioned by the formation of multiple hydrogen bonds within the macrocyclic ring. Me2DOPM forms neutral, mononuclear complexes with all the metals investigated. The presence of hydroxo complexes was observed for Ca2+ and Zn2+ at high pH values. Structural information on the neutral complex [Cu(Me2DO2PME)] has been obtained by a solution X-Band EPR study. It is proposed that Me2DO2PME binds Cu2+ in a distorted octahedral structure using all of its donor atoms, i.e. the four nitrogen atoms and the two phosphonate oxygen atoms. The redox chemistry of [Cu(Me2DO2PME)] in dimethyl sulfoxide and water has been studied by electrochemical measurements. Cyclic voltammetry in DMSO shows the complex to undergo a quasireversible one-electron reduction step leading to an unstable CuI species. 相似文献
73.
Rosanna Bonaccorsi Carlo Petrongolo Eolo Scrocco Jacopo Tomasi 《Theoretical chemistry accounts》1971,20(4):331-342
A model to facilitate the computation of the most stable conformer of associated M · H2O (M being a polar molecule) which depends upon the electrostatic interaction energy between the two associated molecules is proposed and tested. SCF electrostatic potentials for the M molecule and a suitable point charge distribution for H2O were employed in the model computations. Energies predicted by the model are found to be in good agreement with those resulting from an ab initio minimal STO basis SCF treatment of some conformations of the H2O dimer.
Work performed with the financial support of the Consiglio Nazionale delle Ricerche, through its Laboratorio di Chimica Quantistica ed Energetica Molecolare. 相似文献
Zusammenfassung Ein Modell zur Durchführung der Berechnung des stabilsten Konformeren eines Assoziationskomplexes M · H2O, wobei M ein polares Molekül ist, wird vorgeschlagen und untersucht. Es basiert auf der elektrostatischen Wechselwirkung zwischen beiden Partnern, und zwar wird für das Molekül M der elektrostatische Anteil seines SCF-Potentials und für H2O eine angemessene Punktladungsverteilung zugrunde gelegt. Die resultierenden Energien sind in guter Übereinstimmung mit denen, die sich bei einer ab initio Rechnung mit minimaler STO Basis ergeben.
Work performed with the financial support of the Consiglio Nazionale delle Ricerche, through its Laboratorio di Chimica Quantistica ed Energetica Molecolare. 相似文献
74.
Spoto G Gribov E Bordiga S Lamberti C Ricchiardi G Scarano D Zecchina A 《Chemical communications (Cambridge, England)》2004,(23):2768-2769
Cu(I) ions in Cu-ZSM-5 form Cu+(H2) complexes, stable at room temperature and sub-atmospheric H2 pressure, which do not have any homogeneous analogue except for matrix-isolated [Cu(eta2-H2)Cl]. Comparison with the unstable Na+(H2) adducts formed in the parent Na-ZSM-5 zeolite allow the conclusion that the Cu(I)/H2 bond is governed by sigma-pi overlap forces. 相似文献
75.
Tommaso Carofiglio Euro Solari Carlo Floriani Angiola Chiesi-Villa Corrado Rizzoli 《Polyhedron》1996,15(24):4435-4440
The UV-stabilizer 2-(2′-hydroxy-5′-methylphenyl)benzotriazole (Tinuvin P, LH) has been used as a monoanionic bidentate ligand for complexing oxocations. Displacement of acacH from [VO(acac)2] and [MoO2(acac)2] gave [*VO(acac)2*(μ-L)] (2) and [cis-O2Mo(acac)L] (3) respectively, as crystalline compounds. Their structure has been determined by an X-ray analysis showing the structural changes occurring upon coordination. The UV spectrum of Tinuvin P is significantly affected by complexation. 相似文献
76.
Piperidine-, morpholine-4-, N-methylpiperazine-4- and thiornorpholine-4-carbodithioate complexes of chromium(III), manganese(III), tin(II) and lead(II) are prepared and characterized by chemical analyses, spectroscopic methods (I.R. and electronic spectra), magnetic susceptibilities, conductivity measurements and mass spectra. The complexes are of the type M(R2dtc)n, where n is the oxidation number of the metal ion. Where possible a tentative stereochemistry of the complexes is discussed on the basis of the results obtained. In all the complexes the dithiocarbamate ligands show bidentate behaviour. 相似文献
77.
Very simple and selective methods are presented to determine the amino acid tryptophan (Trp) and the biogenic amine tryptamine (Tryp), both compounds with an indole-type molecular structure by the methodology named Heavy Atom Induced-Room Temperature Phosphorescence (HAI-RTP) which constitutes the first time that HAI-RTP has been used to detect compounds with non-naphthalenic structures in their molecules. Different variables affecting the phosphorescence signal (heavy atom perturber and sodium sulfite concentration) were carefully studied. The analytical curves give a linear dynamic range of 15-100 ng ml(-1) and a detection limit of 4 ng ml(-1) for Trp and 94-400 ng ml(-1) and 28 ng ml(-1) for Tryp. The methods have been successfully applied to the analysis of complex food matrices such as the presence of tryptophan in yoghurt and tryptamine in bottled beer. A single alkaline hydrolysis to release Trp from yoghurt proteins and two methods for extracting Tryp from beer samples are proposed and optimised. A total Trp content of 374 mg of Trp per kg of yoghurt was quantified by the standard addition method of calibration and a recovery of 90% was obtained for 250 ng ml(-1) of Tryp in spiked non-alcoholic beer samples. 相似文献
78.
Substoichiometric amorphous thin films of MoO3 in both the transparent and absorptive forms have been studied by X-ray electron spectroscopy. The transparent films can be colored blue (absorptive) electrically or by UV irradiation. The electron distribution curve of the blue film exhibits a small band near the Fermi edge which is absent in the transparent sample. This new band is attributed to electrons trapped in positively charged anion vacancies in the substoichiometric MoO3 lattice. This model provides an interpretation of the electrical conductivity and color of the films. 相似文献
79.
The stereoselective total synthesis of (-)-microcarpalide, a recently discovered 10-membered lactone of fungal origin displaying a remarkable disrupting action on actin microfilaments, was accomplished by using ring-closing metathesis (RCM) as the key step for the formation of the medium-sized ring. The diene ester required for the macrocyclization reaction was assembled via DCC-mediated esterification of two suitable partners, each bearing a terminal alkene group. The alcohol fragment was synthesized from n-bromohexane through a seven-step sequence entailing two consecutive stereoselective homologations of chiral boronic esters as strategic transformations for the sequential insertion of the two stereocentres with the final S absolute configuration, using (+)-pinanediol as the chiral director; final elaboration to the desired C(11) framework envisaged treatment with an allyl Grignard reagent and oxidative cleavage of the boronic scaffold. In contrast, the acidic fragment was prepared in ten steps from d-tartaric acid, whose C(4) backbone was elongated to the required C(7) skeleton by means of two distinct Swern-Wittig oxidation-homologation sequences. 相似文献
80.
Carlo Carlini Emo Chiellini Roberto Solaro 《Journal of polymer science. Part A, Polymer chemistry》1980,18(7):2129-2142
Homogeneous catalytic systems based on optically active low-molecular-weight and macromolecular titanium alcoholates and tri-isobutyl aluminum were used in the isomerization and hydrogenation of chiral and prochiral olefins. The reactions performed in a nitrogen and hydrogen atmosphere show a different behavior in regard to reaction rate, composition of reaction mixture, and stereochemical control. The catalyst based on macromolecular titanium alcoholate displays lower activity and a varying influence on the stereochemical pathway with respect to the catalysts based on low- molecular-weight alcoholates. The data obtained in both cases strongly support the absence of a stereocontrol by the growing chain in the stereoelective polymerization of racemic α-olefins by Ziegler-Natta catalysts based on optically active precursors. Finally evidence is provided in favor of the intermediate step responsible for asymmetric isomerization which does not occur via η-allyl complex. 相似文献