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1.
Jiang W Wanner J Lee RJ Bounaud PY Boger DL 《Journal of the American Chemical Society》2002,124(19):5288-5290
A convergent total synthesis of the ramoplanin A2 and ramoplanose aglycon is disclosed. Three key subunits composed of residues 3-9 (heptapeptide 15), pentadepsipeptide 26, and pentapeptide 34 (residues 10-14) were prepared, sequentially coupled, and cyclized to provide the 49-membered depsipeptide core of the aglycon. Key to the preparation of the pentadepsipeptide 26 incorporating the backbone ester was the asymmetric synthesis of an orthogonally protected L-threo-beta-hydroxyasparagine and the development of effective and near-racemization free conditions for esterification of its hindered alcohol (EDCI, DMAP, 0 degrees C). The coupling sites were chosen to maximize the convergency of the synthesis including that of the three subunits, to prevent late stage racemization of carboxylate-activated phenylglycine-derived residues, and to enlist beta-sheet preorganization of an acyclic macrocyclization substrate for 49-membered ring closure. As such, macrocyclization at the chosen Phe(9)-D-Orn(10) site may benefit from both beta-sheet preorganization as well as closure at a D-amine terminus. Deliberate late stage incorporation of the subunit bearing the labile depsipeptide ester and a final stage Asn(1) side chain introduction provides future access to analogues of the aglycons which themselves are reported to be equally potent or more potent than the natural products in antimicrobial assays. 相似文献
2.
Two approaches to the strigolactone tricyclic lactone skeleton 2 were investigated using ketene/ketene-iminium cycloaddition to olefins. Finally, the first enantioselective access to the four stereoisomers of 5-deoxystrigol 1 is reported using an intramolecular [2+2] cycloaddition of homochiral ketene-iminium salts 5. Very high asymmetric control was achieved with C-2 symmetric pyrrolidines as chiral auxiliary. 相似文献
3.
Yoann Fillâtre David Rondeau Antoine Daguin Alain Jadas-Hecart Pierre-Yves Communal 《Analytical and bioanalytical chemistry》2014,406(5):1541-1550
The determination of 256 multiclass pesticides in lavandin essential oil has been performed by liquid chromatography–electrospray ionization tandem mass spectrometry using the scheduled selected reaction monitoring mode available on a quadrupole-linear ion trap mass spectrometer. With the aim of improving the limits of quantification (LOQs) of the target molecules, a sampling step based on evaporation of the essential oil under a nitrogen flow assisted by controlled heating was tested. The LOQs determined in this case were compared with the values obtained with the classic dilution preparation method. With sampling by dilution, 247 pesticides were detected and quantified at low concentration, with 74 % of the pesticides having LOQs of 10 μg L-1 or less. With the evaporation method, a global improvement of the LOQs was observed, with lower LOQs for 92 active substances and LOQs of 10 μg L-1 or less for 82.8 % of the pesticides. Almost twice as many active substances had an LOQ of 1 μg L-1 or less when the evaporation method was used. Some pesticides exhibited poor recovery or high variance caused by volatilization or degradation during the evaporation step. This behavior was evidenced by the case of thiophanate-methyl, which is degraded to carbendazim. Figure
Sampling method by dilution or evaporation in the multiresidue determination of pesticides in essential oils by LC/MS 相似文献
4.
Antoine Bardin Pierre-Yves Le Gac Hervé Bindi Bruno Fayolle 《Journal of polymer science. Part A, Polymer chemistry》2020,58(22):3170-3182
This publication highlights the structure–property relationships in several thermoplastic elastomers (TPEs): one poly(ether-block-amide) and two thermoplastic polyurethane elastomers with ester and ether soft blocks. Structural changes are induced by chemical degradation from virgin samples through hydrolysis and oxidation. Molar mass measurements show an exclusive chain scission mechanism for all TPEs, regardless of the chemical modification condition. Mechanical behavior was nevertheless obtained from uniaxial tensile testing and fracture testing while considering the essential work of fracture (EWF) concept. During the macromolecular scission process, elongation at break shows a plateau followed by a drop, while stress at break decreases steadily. Once again, the trend is identical for all TPEs in all conditions considered. The βwp parameter determined using the EWF concept exhibits an interesting sensitivity to scissions (i.e., molar mas decrease). Plotting elongation at break as a function of molar mass reveals a strong correlation between these two parameters. This master curve is particularly remarkable considering the range of TPEs and chemical breakdown pathways considered (hydrolysis and oxidation at several temperatures). Relevant structure–property relationships are proposed, highlighting that molar mass is a predominant parameter for determining the mechanical properties of thermoplastic elastomers. 相似文献
5.
Orain PY Capon JF Kervarec N Gloaguen F Pétillon F Pichon R Schollhammer P Talarmin J 《Dalton transactions (Cambridge, England : 2003)》2007,(34):3754-3756
Treatment of [Fe(2)(micro-pdt)(CO)(6)] (pdt = S(CH(2))(3)S) with 1,10-phenanthroline (phen) in refluxing toluene affords the asymmetric complex [Fe(2)(micro-pdt)(CO)(4)(phen)] (1); the protonation of with HBF(4).OEt(2) in CD(2)Cl(2) at 203 K has been monitored by (1)H NMR. 相似文献
6.
Ouali N Bocquet B Rigault S Morgantini PY Weber J Piguet C 《Inorganic chemistry》2002,41(6):1436-1445
Variable-temperature (1)H and (13)C NMR measurements of the D(3)-symmetrical triple-helical complexes [Ln(L1-2H)(3)](3)(-) (L1 = pyridine-2,6-dicarboxylic acid; Ln = La-Lu) show evidence of dynamic intermolecular ligand-exchange processes whose activation energies depend on the size of the metal ion. At 298 K, the use of diastereotopic probes in [Ln(L3-2H)(3)](3)(-) (L3 = 4-ethyl-pyridine-2,6-dicarboxylic acid) shows that fast intramolecular P <==> M interconversion between the helical enantiomers occurs on the NMR time scale. Detailed analyses of the paramagnetic NMR hyperfine shifts according to crystal-field independent techniques demonstrate the existence of two different helical structures, one for large lanthanides (Ln = La-Eu) and one for small lanthanides (Ln = Tb-Lu), in complete contrast with the isostructurality proposed 25 years ago. A careful reconsideration of the original crystal-field-dependent analysis shows that an abrupt variation of the axial crystal-field parameter A(0)2 parallels the structural change leading to some accidental compensation effects that prevent the detection of structural variations according to the classical one-nucleus method. Crystal structures in the solid state and density functional theory calculations in the gas phase provide structural models that rationalize the paramagnetic NMR data. A regular triple-helical structure is found for small lanthanides (Ln = Tb-Lu) in which the terdentate chelating ligands are rigidly tricoordinated to the metals. A flexible and distorted structure is evidenced for Ln = La-Eu in which the central pyridine rings interact poorly with the metal ion. The origin of the simultaneous variation of structural parameters and crystal-field and hyperfine constants near the middle of the lanthanide series is discussed together with the use of crystal-field-independent techniques for the interpretation of paramagnetic NMR spectra in axial lanthanide complexes. 相似文献
7.
Pierre-Yves Roger Fabien Blondeau David Bensa Thierry Constantieux Jean Rodriguez 《Molecular diversity》2009,13(4):469-473
A new one-pot domino reaction for a general entry to functionalised bridged bicyclo[n.2.1] ring systems from α ,α’-diactivated cyclic ketones and trans-1,4-dihalides is described. The sequence combines a base promoted C–O cycloalkylation reaction leading to fused polycyclic
enol ethers and their in situ palladium-catalysed isomerisation. 相似文献
8.
[reaction: see text] Nitronic acids undergo an intramolecular 1,3-dipolar cycloaddition to unactivated double bonds, and the resulting isoxazolidines spontaneously evolve by an unprecedented in situ oxidative ring cleavage. The extension of this transformation to silyl nitronates results in a general diastereoselective construction of hydroxymethyl nitro functionalized tetrahydro-furans and -pyrrolidine having up to four consecutive stereogenic centers. 相似文献
9.
Fran?ois?NicotEmail author Luc?Sibille Pierre-Yves?Hicher 《Continuum Mechanics and Thermodynamics》2015,27(1-2):173-193
When granular materials are subjected to proportional strain loading paths, they manifest a variety of behaviors depending on the initial void ratio of the specimen as well as the imposed dilatancy/contractancy rate. In some cases, the stress components may vanish over the duration of the test, and the specimen may progressively liquefy. To investigate this behavior, the authors have developed a kinematic approach to be deployed in two parts. First, numerical simulations are performed by means of a discrete element method. Secondly, two micromechanical models have corroborated the DEM results. The performance of these models may explain a number of microstructural mechanisms responsible for the macroscopic constitutive behavior. 相似文献
10.