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171.
Guimond-Tremblay J Gagnon MC Pineault-Maltais JA Turcotte V Auger M Paquin JF 《Organic & biomolecular chemistry》2012,10(6):1145-1148
The synthesis of three monofluorinated dimyristoylphosphatidylcholine derivatives (F-DMPC), with the fluorine atom located on the acyl chain in position 2 of the glycerol (sn-2) is described. The synthetic strategy relies on the coupling of 1-myristoyl-2-hydroxy-sn-glycero-3-phosphocholine (lyso-PC) and three different fluorinated fatty acids. The latter were obtained from two different and complementary synthetic routes. Preliminary FTIR studies suggest that the presence of the fluorine atom does not significantly perturb the lipid conformational order and phase transition temperature and that these monofluorinated PC derivatives could be used as probes for the study of membrane topology, i.e. the location of drugs, peptides or proteins in membranes. 相似文献
172.
A new approach to total syntheses of piperidine alkaloids (+)-241D, isosolenopsin and isosolenopsin A has been developed from D-alanine. The key step to access the chiral pyridinone intermediate was achieved via a gold mediated cyclization. Finally, various reduction conditions afforded the natural products in few steps and good overall yields. 相似文献
173.
Chatgilialoglu C Mozziconacci O Tamba M Bobrowski K Kciuk G Bertrand MP Gastaldi S Timokhin VI 《The journal of physical chemistry. A》2012,116(29):7623-7628
The reactions of α-hydroxyl and α-alkoxyl alkyl radicals with methanesulfonyl chloride (MeSO(2)Cl) have been studied by pulse radiolysis at room temperature. The alkyl radicals were produced by ionizing radiation of N(2)O-saturated aqueous solution containing methanol, ethanol, isopropanol, or tetrahydrofuran. The transient optical absorption spectrum consisted of a broad band in the region 280-380 nm with a maximum at 320 nm typical of the MeSO(2)(?) radical. The rate constants in the interval of 1.7 × 10(7)-2.2 × 10(8) M(-1) s(-1) were assigned to an electron-transfer process that leads to MeSO(2)Cl(?-), subsequently decaying into MeSO(2)(?) radical and Cl(-). The rate constants for the addition of CH(3)SO(2)(?) to acrolein and propiolic acid were found to be 4.9 × 10(9) M(-1) s(-1) and 5.9 × 10(7) M(-1) s(-1), respectively, in aqueous solutions and reversible. The reactivity of tosyl radical (p-CH(3)C(6)H(4)SO(2)(?)) toward a series of alkenes bearing various functional groups was also determined by competition kinetics in benzene. The rate constants for the addition of tosyl radical to alkenes vary in a much narrower range than the rate constants for the reverse reaction. The stabilization of the adduct radical substantially contributes to the increase of the rate constant for the addition of tosyl radical to alkenes and, conversely, retards the β-elimination of tosyl radical. 相似文献
174.
Góngora-Benítez M Cristau M Giraud M Tulla-Puche J Albericio F 《Chemical communications (Cambridge, England)》2012,48(17):2313-2315
A new universal strategy exploits DKP formation in a dipeptide moiety whose C-terminal residue is blocked by a leaving group. It enables both synthesis of C-terminal protected peptides that are useful for convergent synthesis of large peptides and use of a C-terminal permanent protecting group that can be cleaved by catalytic hydrogenation to release the peptide. 相似文献
175.
Fernanda Trombetta da Silva Natália Fanti Panno Michèle Oberson de Souza Roberto Fernando de Souza Emilse Maria Agostini Martini 《Journal of Solid State Electrochemistry》2012,16(10):3237-3244
Electrochemical studies were performed using Ni electrodes in solutions of a mixture of ethylene glycol or of γ-butyrolactone with 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid. The aim of the study was to evaluate the use of these systems in electrochemical double-layer capacitor. Cyclic voltammetry experiments showed a potential range at which the Ni electrode behaved as a polarizable electrode. Ni oxidizes at high anodic potentials. Inside the potential range without electrochemical activity, the capacitance and the solution resistance, which were evaluated by impedance electrochemical spectroscopy, were compared for the two solutions tested. Conductivity measurements of the electrolytes with different compositions were also acquired. The results of cyclic voltammetry indicated that the Ni has a wide electrochemical window and low current peak densities of oxidation in the γ-butyrolactone medium than in ethylene glycol medium. The γ-butyrolactone and 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid solutions had the highest conductivity values. Decreased 1-n-butyl-3-methylimidazolium tetrafluoroborate ionic liquid content in different solvent mixtures resulted in an increase in the capacitance value at the Ni/electrolyte interface. The highest capacitance values were obtained for Ni in ethylene glycol and 1-n-butyl-3-methylimidazolium tetrafluoroborate medium. 相似文献
176.
Detailed analysis of the vibronic structure in the electronic absorption spectrum of Cs2NaYbF6 at temperatures between 10 and 300 K enables the crystal field energy level diagram of Yb3+ in this cubic host to be deduced. Ultraviolet and visible laser excitation of Cs2NaYbF6, Cs2NaY(0.9)Yb(0.1)F6, and Cs2NaHo(0.99)Yb(0.01)F6 give spectral features mainly due to Yb3+ being situated at a range of defect sites. The 4f13 crystal field analyses of octahedral YbX6(3-) (X = F, Cl, Br) systems show the expected trends in parameter values, but the energy level fits are poor. Inclusion of the interaction with the charge-transfer configuration 4f14np5 provides an exact fitting of energy levels for YbX6(3-), and a smooth variation of ff and fp crystal field parameters for Cs2NaLnCl6 (Ln = Er, Tm, Yb) is observed. 相似文献
177.
Canac Y Conejero S Soleilhavoup M Donnadieu B Bertrand G 《Journal of the American Chemical Society》2006,128(2):459-464
Only basic phosphines, such as tris(dimethylamino)phosphine, allow for the synthesis of a stable acyclic beta-amino phosphonium salt 1c, which upon deprotonation with butyllithium affords the corresponding stable C-amino phosphorus ylide 2c. In contrast, cyclic beta-amino phosphonium salts 5a and 5b are stable despite the presence of weakly basic triarylphosphine fragments. They are prepared by intramolecular insertion of the carbene center of (amino)(phosphonio)carbenes into the CH bond of a phosphorus substituent. Deprotonation of 5a leads to the corresponding cyclic C-amino phosphorus ylide 6a, which has been fully characterized including an X-ray diffraction study. Deprotonation of 5b affords enamine 8, probably via fragmentation of ylide 6b into transient carbene 7b and a subsequent 1,2-hydrogen shift. Transient cyclic C-amino phosphorus ylides 6c and 6d have been prepared by intramolecular addition of a carbanion generated by deprotonation of a phosphorus substituent. Three-membered heterocycle 6c rearranges into alkene 9, whereas the four-membered ring system undergoes a ring opening affording the stable carbene 7d. The latter results pave the route for the synthesis of various mixed carbene-phosphine bidentate ligands. 相似文献
178.
Escoubet S Gastaldi S Vanthuyne N Gil G Siri D Bertrand MP 《The Journal of organic chemistry》2006,71(19):7288-7292
The racemization of nonactivated aliphatic amines has been mediated with alkanethiols and with methyl thioglycolate in the presence of AIBN. The process involves reversible H-abstraction at the chiral center, in a position alpha relative to nitrogen, by thiyl radical. The knowledge of the reaction enthalpy is critical to select the appropriate thiol. In the absence of experimental values, theoretical calculations of the alpha-C-H BDEs and the S-H BDE provide a useful guide. 相似文献
179.
Mohamed-Benkada M Montagu M Biard JF Mondeguer F Verite P Dalgalarrondo M Bissett J Pouchus YF 《Rapid communications in mass spectrometry : RCM》2006,20(8):1176-1180
The production of peptaibols by a marine-related Trichoderma longibrachiatum strain was studied using electrospray ionisation multiple-stage ion trap mass spectrometry (ESI-MSn-IT) and gas chromatography/electron impact mass spectrometry (GC/EI-MS). Two major groups of peptaibols were identified, those with long sequences (20 amino acids) and others with short sequences (11 amino acids). This paper describes the methodology used to establish the sequences of short peptaibols in a mixture without previous individual separation. Nine peptaibols were identified. Among them, eight are new, namely as trichobrachin A I-IV (Aib9-Pro10 sequence) and as trichobrachin B I-IV (Val9-Pro10 sequence). Original Pro6-Val7 and Val9-Pro10 sequences have to be noted. 相似文献
180.
The synthesis of stable and highly organized phenanthroline, terpyridine, and pyridino-oxazoline ligands bearing one or two 4-methyl-3,5-diacylaminophenyl modules equipped with two lateral dialkoxyphenyl groups has been performed using EDC.HCl and DMAP reagents in the final coupling reaction. Evidently, in the final ligands and in the solid state intermolecular hydrogen bonding maintains the coherence of the tridimensional structure as clearly evidenced by FT-IR and X-ray diffraction spectroscopy in the cases of the methoxy ligands. The supramolecular packing is also maintained by additional pi-pi stacking interactions. 相似文献