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81.
82.
David R. Benson Robert Valentekovich Suk-Wah Tam Franois Diederich 《Helvetica chimica acta》1993,76(5):2034-2060
Following a known synthetic procedure, the porphyrin-cyclophane 1 having a porphyrin attached by two straps to an apolar cyclophane binding site was prepared. Upon metallation, the ZnII and FeIII derivatives 2 and 3 , respectively, were obtained in good yields. Treatment of 3 with base yielded the μ-oxo dimer 4 in which the two oxo-bridged porphyrins moieties are both capped by cyclophane binding sites. All compounds 1–4 are freely soluble in protic solvents such as MeOH and CF3CH2OH, and the FeIII derivatives 3 and 4 are active cytochrome P-450 mimics in these protic environments. Strong inclusion complexation of polycyclic aromatic hydrocarbons by 1 and 3 in alcoholic solvents was observed and quantified by 1H-NMR and UV/VIS titrations. Acenaphthylene binds in an ‘equatorial’ orientation which locates its reactive 1,2-double bond near the porphyrin center, whereas phenanthrene binds ‘axially’ with the reactive 9,10-double bond oriented away from the porphyrin. The reduction potential of 3 was not significantly altered by substrate binding. In the unbound form, the FeIII center in porphyrin 3 was found by ESR and 1H-NMR to prefer a high-spin state (S = 5.2). In CF3CH2OH, using iodosylbenzene as O-transfer agent, the FeIII derivative 3 catalyzed the oxidation of acenaphthylene to acenaphthen-1-one ( 14 ). Phenanthrene inhibited the reaction, possibly as a result of strong but nonproductive binding. Under similar conditions, isotetralin ( 18 ) was aromatized with high turnover to 1,4-dihydronaphthalene. The μ-oxo dimer 4 also showed high activity in the oxidation of acenaphthylen in MeOH, a result which provides strong evidence for efficent supramolecular catalysis. Due to as yet unknown reaction channels leading to polymeric products, poor mass balances were generally obtained in the oxidations effected in MeOH and CF3CH2OH in the presence of PhIO. 相似文献
83.
François Couty François Durrat Gwilherm Evano Damien Prim 《Tetrahedron letters》2004,45(40):7525-7528
A synthesis of stereodefined enantiomerically pure 2-alkenyl azetidines is described using Wittig olefination as key step. The quaternary triflate ammonium salts of these heterocycles were prepared in a stereoselective way and treatment of these azetidinium salts with a base (KHMDS or PhLi) induced a regioselective Stevens rearrangement leading to a 3-alkenyl pyrrolidine. An unprecedented SN2′ reaction involving phenyllithium as nucleophile and an ammonium as leaving group was observed in one case. 相似文献
84.
Hydrogen-aarbonyl chelation and magnesium-arene π coordination are proposed to aooount for enhanced enantioselectivïty in 1,4-addition reactions of chiral cuprates. 相似文献
85.
Bertrand Pierre Broniatowski Michel Marcotorchino Jean-François 《Advances in Data Analysis and Classification》2022,16(4):1069-1093
Advances in Data Analysis and Classification - This paper aims at comparing two coupling approaches as basic layers for building clustering criteria, suited for modularizing and clustering very... 相似文献
86.
Fangzin Fu Hongyu Li Dongsheng Zhu Qunxin Fang Huade Pan Edward R. T. Tiekink Franois Kayser Monique Biesemans Ingrid Verbruggen Rudolph Willem Marcel Gielen 《Journal of organometallic chemistry》1995,490(1-2):163-171
The synthesis and characterization by 1H, 13C, 119Sn NMR and 119Sn Mössbauer spectroscopy of (Z)-1-[2-(triphenylstannyl)vinyl]-1-cycloheptanol,
(1), and (Z)-1-[2-tri-p-tolylstannyl)vinyl-1-cycloheptanol,
(2), are described, together with their halodemetallation by I2, Br2 and ICIl to yield derivatives of the types
(Ar = phenyl or p-tolyl, N = 1, 2; X = I, Br, Cl, respectively). The solid-state structures of four compounds have been determined by X-ray diffraction analysis. In the crystals of
(1) and
(2) the Sn atom has a tetrahedral geometry distorted towards trigonal bipyramid as a consequence of a close intramolecular contact with the hydroxyl O(1) atom of 2.742(3) Å and 2.768(3) Å, respectively. A trigonal bipyramidal geometry is found in
(12) and
(4), in which significant Sn---O(1) interactions are noted [2.437(8) Å and 2.407(8) Å, respectively]. 相似文献
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87.
Lépine F Milot S Déziel E He J Rahme LG 《Journal of the American Society for Mass Spectrometry》2004,15(6):862-869
The opportunistic pathogen Pseudomonas aeruginosa produces a large array of 4-hydroxy-2-alkylquinolines (HAQs). These compounds were analyzed by LC/MS, using positive electrospray ionization, in the culture supernatant of strain PA14. Fifty-six HAQs and related compounds were detected and their [M + H](+) ions were further analyzed by collision induced dissociation (CID). These HAQs were grouped into five different series based on the presence of an hydrogen or hydroxyl group at the 3 position, an N-oxide group in place of the quinoline nitrogen, and an unsaturation on their alkyl side chain. Two new analogs of 3,4-dihydroxy-2 heptylquinoline, the Pseudomonas quinolone signal (PQS), were found with an alkyl chain longer by one and two methylene groups. Moreover, two additional series of compounds were identified in which a saturated or unsaturated alkyl side chain is located at the 3 position along with an hydroxyl group at the 3 position and a ketone at the 2 position. No HAQ N-oxides, nor any compounds from the latter two series, were detected in a pqsL mutant derivative of PA14, indicating that this gene is involved in the biosynthesis of these compounds. This work demonstrates the large repertoire of HAQ and HAQ-related compounds produced by P. aeruginosa, and provides insight into N-oxides biosynthesis and confirm the hypothesis that N-oxides are the precursors of compounds from Series 6 and 7. 相似文献
88.
89.
Meng M Stievano L Lambert JF 《Langmuir : the ACS journal of surfaces and colloids》2004,20(3):914-923
Glycine was adsorbed on the surface of a well-defined silica from aqueous solutions of variable concentrations and pHs. The adsorbed molecules were characterized using middle-IR and UV-vis-NIR spectroscopies. Except at the lowest pH (2.0), they were predominantly present on the surface as zwitterions. Two successive deposition mechanisms were evidenced with increasing glycine concentration. At low concentrations, glycine is specifically adsorbed on silica surface sites, probably through its NH3+ moiety. The pH dependence suggests that these sites may be silanolate groups (approximately equal to Si-O-). At higher concentrations, specific adsorption sites are saturated and surface-induced precipitation of beta-glycine is observed. The thermal reactivity of adsorbed/deposited glycine was then investigated by thermogravimetric analysis, in situ diffuse reflectance IR spectroscopy, and thermoprogrammed desorption coupled with mass spectrometry. Adsorbed glycine molecules react to form peptide bonds at a temperature considerably lower than that for bulk crystalline alpha-glycine. The main reaction product is the cyclic dimer diketopiperazine, with no evidence of the linear dimer. The activation mechanism is not diffusionally limited; the formation of "surface acyls", previously proposed for related systems, has not been evidenced here. These findings are of relevance for the evaluation of prebiotic peptide synthesis scenarios. 相似文献
90.
Mathieu D Frapart YM Bartoli JF Boucher JL Battioni P Mansuy D 《Chemical communications (Cambridge, England)》2004,(1):54-55
Electron transfer from tetrahydropterins to iron porphyrins, with formation of intermediate tetrahydropterin cation radicals, is a very general reaction that was shown to occur not only with tetrahydrobiopterin, as originally found in NO-synthases, but also with another important biological cofactor, tetrahydrofolate, and various iron porphyrins, either in their ferric state, or in the Fe(II)O(2) state, as in the first model of the corresponding NO-synthase reaction described in this paper. 相似文献