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排序方式: 共有185条查询结果,搜索用时 15 毫秒
1.
Takayasu Yamauchi Hiroyuki Sazanami Yuuichi Sasaki Kimio Higashiyama 《Tetrahedron》2005,61(7):1731-1736
1,3-Oxazolidines were easily obtained by condensation of N-substituted (R)-phenylglycinol with aldehydes. Addition of organolithium reagents to 1,3-oxazolidines by complexation with the bulky Lewis acid aluminum tris(2,6-diphenylphenoxide) (ATPH) readily produced the corresponding chiral amines with good yield and high diastereoselectivity. The configuration of the new stereogenic center was shown to be opposite to that of adducts obtained for the same 1,3-oxazolidines using Grignard reagents. The best diastereoselectivity was achieved using N-isopropyl-1,3-oxazolidines. The mechanism of addition was deduced by determining the stereochemistry of the iminium-aluminum complex by NOE experiments. 相似文献
2.
Yan Wu LI Liang HUANG* Institute of Materia Medica Chinese Academy of Medical Sciences & Peking Union Medical College Beijing 《中国化学快报》2002,13(10)
The natural product, hainanolide 1, also under the name harringtonolide2 demonstrated antitumor and antiviral activities in preliminary test. Its structure was determined by X-ray diffraction. The total synthesis of 1 was reported recently by Mander3. A different scheme of its synthesis has been studied in our laboratory4. Here the determination of the stereochemical structure of the key intermediate 2 in the synthesis was reported. HMBC and HMQC spectra identified the skeleton and H,… 相似文献
3.
Two-dimensional (2D) NMR is an invaluable technique for the complete analysis and assignment of chemical structures. Although 19F/19F COSY experiments are routinely used for assignments in perfluorochemicals, interpretation can be difficult because four-bond (4JFF) coupling constants are typically 5-10-fold larger than vicinal (3JFF) coupling constants. Furthermore, the dependence of long range coupling constants on stereochemistry is not always known. Fluorine-fluorine NOESY correlations represent an enhancement in the arsenal of 2D 19F NMR experiments. The NOESY and COSY spectra of 2,2,3,3,4,4,4-heptafluorobutanol and a telomeric perfluorochemical iodide show that COSY identifies the 1,4-fluorine interactions whereas NOESY identifies the vicinal fluorine atoms. The combined experiments have been used to unambiguously assign all of the fluorines in a mixture of cis- and trans-perfluoro-1,3-dimethylcyclohexane and in a substituted perfluorotetrahydrofuran. 相似文献
4.
Molecular dynamics simulations of cyclosporin A: The crystal structure and dynamic modelling of a structure in apolar solution based on NMR data 总被引:1,自引:0,他引:1
J. Lautz H. Kessler R. Kaptein W. F. van Gunsteren 《Journal of computer-aided molecular design》1987,1(3):219-241
Summary The conformation of the immunosuppressive drug cyclosporin A (CPA), both in apolar solution and in crystalline state, has been studied by computer simulation techniques. Three molecular dynamics (MD) simulations have been performed: one modelling the crystal structure and two modelling the structure in apolar solution, using a restrained MD approach in which data from nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy are taken into account. The simulation of the crystalline state (MDC) concerns a system of 4 unit cells containing 16 cyclosporin A molecules and 22 water molecules, which is simulated using crystalline periodic boundary conditions. The simulations modelling the apolar solvent conformation (MDS) concern one isolated cyclosporin A molecule. In these simulations an extra term in the interatomic potential function is used, which forces the molecule to satisfy a set of 57 atom-atom distance constraints originating from nuclear Overhauser effects (NOEs) obtained from NMR spectroscopy and one distance constraint deduced from IR spectroscopy.From a comparison of the results of the crystal simulation to those of the X-ray experiment in terms of structure, atomic fluctuations, hydrogen bond pattern, etc., it is concluded that the force field that is used yields an adequate representation of crystalline cyclosporin A. Secondly, it is shown that the dynamic modelling technique that is used to obtain a structure in a polar solution from NMR distance information works well. Starting from initial conformations which have a root mean square difference of 0.14 nm both distance restrained MD simulations converge to the same final solution structure. A comparison of the crystal structure of cyclosporin A and the one in apolar solution shows that there are significant differences. The overall difference in atomic positions is 0.09 nm for the Cx atoms and 0.17 nm for all atoms. In apolar solution, the molecule is slightly more bent and the side chains of 1 MeBmt and 10 MeLeu adopt a different conformation.Abbreviations MeBmt
(4R)-4[(E)-2-butenyl]-4-methyl-l-Threonine
- MD
Molecular dynamics
- EM
Energy minimization
- MDC
Molecular dynamics simulation of the crystal
- MDS1
Restrained molecular dynamics simulation to obtain the structure in solution starting from the crystal structure
- MDS2
Like MDS1, but starting from the SMS structure
- SMS
Proposed structure in solution, obtained by model building
- XRAY
An X-ray structure
- CPA
Cyclosporin A
- NMR
Nuclear magnetic resonance spectroscopy
-
NOE
Nuclear Overhauser enhancement
-
MDS1
Mean simulated structure obtained by averaging over the time period 20–40 ps of the MDS1 simulation
- MDS2
Mean simulated structure obtained by averaging over the time period 10–30 ps of the MDS2 simulation
-
Mean simulated structure obtained by averaging over the time period 7–15 ps and over the 16 asymmetric units in the computational box of the MDC simulation. 相似文献
5.
6.
Summary For visual analysis of the density reorganization and distortion, the one-dimensional cut (x, y
0,z
0) and the two-dimensional cut (x, y, z
0) of the three-dimensional electron density difference function (x, y, z) are frequently employed. However, these cut functions do not satisfy any sum rules in contrast to the original difference function (x, y, z). To avoid this difficulty, the use of the marginal electron density functions
x
(x) and
xy
(x, y) and their difference functions
x
(x) and
xy
(x, y) is proposed. The marginal densities are condensation of the three-dimensional density onto a particular plane or line of our interest, and they satisfy the sum rule (i.e., the conservation of the number of electrons) exactly. Some basic properties of the marginal electron density are clarified for typical diatomic molecular orbitals. An illustrative application is given for the bonding and antibonding processes in the H2 system. 相似文献
7.
The heteronuclear cross-relaxation rates in polymers were determined by selective and conventional ~(13)C spin-lattice relaxation experiments, the proton-carbon distances were calculated by the theoretical formula, and two-dimensional NOE spectra of the polymers were also measured. The results showed that (1) the measured proton-carbon distances coincide with the distances from molecular models, (2) there is the observable dipolar cross-relaxation effect between the quaternary carbons and their neighboring protons, and (3) the optimum mixing times depend on the relaxation properties of the proton and carbon. 相似文献
8.
9.
Katritzky AR Akhmedov NG Wang M Rostek CJ Steel PJ 《Magnetic resonance in chemistry : MRC》2004,42(7):648-658
The 1H and 13C NMR spectra of compounds 1-11 and 16-22 in CDCl3 and DMSO-d6 solutions allowed structural assignment to regioisomers 1/5 and 2/6 and their regioselective cyclization products 16-18 utilizing one- and two-dimensional NMR techniques (APT, DEPT, NOE difference, COSY, NOESY, HETCOR and gHMQC, gHMBC). Temperature-dependent 1H NMR spectra of 8-anilino-5-(4-methyl-2-pentyl)-2,3-dihydro-1,5-benzothiazepin-4(5H)-one (18) indicated a free energy of activation (deltaG++) of ca 17 kcal mol(-1) for interconversion between rotamers. The 1H and 13C NMR spectra of 20 and 22 containing two chiral centers exhibit duplication of several signals, indicating the existence of two diastereomeric forms. The structure of 4 was unambiguously confirmed by x-ray crystallography. 相似文献
10.
When a benzene ring bears two 2-methyl-1-naphthyl moieties in the para, meta or ortho positions as in 1,4-bis(2-methyl-1-naphthyl)benzene, 1, 1,3-bis(2-methyl-1-naphthyl)benzene, 2 and 1,2-bis(2-methyl-1-naphthyl)benzene 3, two rotational isomers (atropisomers) are generated, with the two naphthyl substituents in a syn or anti relationship. In the case of the para and meta derivatives (1 and 2, respectively) these atropisomers could not be separated but were detected by NMR spectroscopy, that also allowed the determination of their syn-anti interconversion barriers in solution (19.5 and 20.4 kcal mol−1, respectively) and, in the case of 2, also in the solid state (26.7 kcal mol−1). In the more hindered ortho derivative 3, the syn (meso) and anti (racemic) atropisomers interconvert in solution with a barrier (31.2 kcal mol−1) sufficiently high to allow their physical separation. The racemic form could also be separated (by enantioselective HPLC) into the PP and MM enantiomers. Analysis of the corresponding CD spectra allowed the assignment of the absolute configuration. When three such naphthyl substituents are bonded to the phenyl in a meta relationship, two atropisomers in statistical proportions were observed: the anti (Cs symmetry) and the syn (C3v symmetry) display a 3:1 ratio at the equilibrium in solution. This ratio is different in the solid state, as is the interconversion barrier (22.1 and 32.1 kcal mol−1 in solution and in the solid, respectively). 相似文献