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1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
2.
Alvaro Carrillo Ravi S. Kane 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3352-3359
This article describes the formation and characterization of self‐assembled nanoparticles of controlled sizes based on amphiphilic block copolymers synthesized by ring‐opening metathesis polymerization. We synthesized a novel hydrophobic derivative of norbornene; this monomer could be polymerized using Grubbs' catalyst [Cl2Ru(CHPh)(PCy3)2] forming polymers of controlled molecular weight. We synthesized amphiphilic block copolymers of controlled composition and showed that they assemble into nanoparticles of controlled size. The nanoparticles were characterized using dynamic light scattering and transmission electron microscopy. Tuning the composition of the block copolymer enables the tuning of the diameters of the nanoparticles in the 30‐ to 80‐nm range. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3352–3359, 2004 相似文献
3.
C. Sparber J. A. Carrillo J. Dolbeault P. A. Markowich 《Monatshefte für Mathematik》2004,141(3):237-257
We analyze the long-time behavior of transport equations for a class of dissipative quantum systems with Fokker-planck type diffusion operator, subject to confining potentials of harmonic oscillator type. We establish the existence and uniqueness of a non-equilibrium steady state for the corresponding dynamics. Further, using a (classical) convex Sobolev inequality, we prove an optimal exponential rate of decay towards this state and additionally give precise dispersion estimates in those cases, where no stationary state exists. 相似文献
4.
Summary We study the integration theory for general integral metrics when restricted to upper integrals q, finding improvements in the relation between the classes of the q-integrable and the ql-integrable functions. We give new results and notions which lead to the desirable characterizations of q-integrable functions as ql-integrable f with q(|f|) < ∞, and of ql-integrable functions via the integrability of their upper truncations, under natural conditions which are fulfilled in most
finitely additive integration theories. 相似文献
5.
We analyze the well-posedness of the initial value problem for the dissipative quasi-geostrophic equations in the subcritical
case. Mild solutions are obtained in several spaces with the right homogeneity to allow the existence of self-similar solutions.
While the only small self-similar solution in the strong
Lp{\cal L}^{p}
space is the null solution, infinitely many self-similar solutions do exist in weak-
Lp{\cal L}^{p}
spaces and in a recently introduced [7] space of tempered distributions. The asymptotic stability of solutions is obtained
in both spaces, and as a consequence, a criterion of self-similarity persistence at large times is obtained. 相似文献
6.
We quantify the long-time behavior of solutions to the nonlinear Boltzmann equation for spatially uniform freely cooling inelastic Maxwell molecules by means of the contraction property of a suitable metric in the set of probability measures. Existence, uniqueness, and precise estimates of overpopulated high energy tails of the self-similar profile proved in ref. 9 are revisited and derived from this new Liapunov functional. For general initial conditions the solutions of the Boltzmann equation are then proved to converge with computable rate as t → ∞ to the self-similar solution in this distance, which metrizes the weak convergence of measures. Moreover, we can relate this Fourier distance to the Euclidean Wasserstein distance or Tanaka functional proving also its exponential convergence towards the homogeneous cooling states. The findings are relevant in the understanding of the conjecture formulated by Ernst and Brito in refs. 15, 16, and complement and improve recent studies on the same problem of Bobylev and Cercignani(9) and Bobylev, Cercignani and one of the authors.(11) 相似文献
7.
Lourdes Callau Marta Giamberini Jos Antonio Reina Ana Mantecn 《Journal of polymer science. Part A, Polymer chemistry》2006,44(6):1877-1889
The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P4 and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and 1H and 13C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C2 mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006 相似文献
8.
Suńol J. J. Saurina J. Carrillo F. Colom X. 《Journal of Thermal Analysis and Calorimetry》2003,72(2):753-758
Comparison of Lyocell, modal and viscose fibers was performed by means of differential scanning calorimetry, thermogravimetry
and scanning electron microscopy. Thermal analysis was performed in air atmosphere. Samples were mercerized (21.3 g 100 mL-1)
or submitted to solar radiation (seven months). Solar degraded samples presents a higher thermal stability and are initially
less degraded. Furthermore, Lyocell fiber is the most stable under thermal degradation conditions. Heating produces a reduction
of the fiber diameter (about 50%).
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
9.
JPC – Journal of Planar Chromatography – Modern TLC - The dansyl derivatives of N-nitrosodimethylamine, N-nitrosodi-ethylamine, and N-nitrosodibuthylamine have been separated by HPTLC... 相似文献
10.
Sannomiya M Rodrigues CM Coelho RG dos Santos LC Hiruma-Lima CA Souza Brito AR Vilegas W 《Journal of chromatography. A》2004,1035(1):47-51
The methanolic extract of the leaves of the medicinal plant Byrsonima crassa (Malpighiaceae) contain flavonoids with antioxidant activity. They were separated in a preparative scale using high-speed counter-current chromatography. The optimum solvent system used was composed of a mixture of ethyl acetate-n-propanol-water (140:8:80 (v/v/v)) and led to a successful separation between monoglucosilated flavonoids (quercetin-3-O-alpha-L-arabinoside, quercetin-3-O-beta-D-galactoside) and the biflavonoid amentoflavone in only 3.5 h. The purities of quercetin-3-O-alpha-L-arabinoside (95 mg), quercetin-3-O-beta-D-galactoside (16 mg) and the biflavonoid amentoflavone (114 mg) were all isolated at purity over 95%. Identification was performed by 1H NMR, 13C NMR and UV analyses. 相似文献