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11.
Dr. Szilárd Varga Péter Angyal Gábor Martin Dr. Orsolya Egyed Dr. Tamás Holczbauer Dr. Tibor Soós 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13649-13653
We report 8-step syntheses of (−)-minovincine and (−)-aspidofractinine using easily available and inexpensive reagents and catalyst. A key element of the strategy was the utilization of a sequence of cascade reactions to rapidly construct the penta- and hexacyclic frameworks. These cascade transformations included organocatalytic Michael-aldol condensation, a multistep anionic Michael-SN2 cascade reaction, and Mannich reaction interrupted Fischer indolization. To streamline the synthetic routes, we also investigated the deliberate use of steric effect to secure various chemo- and regioselective transformations. 相似文献
12.
Demeter Krupka 《Reports on Mathematical Physics》1974,5(3):355-360
The notion of generalized invariant transformations of variational problems in Lagrangian formulation is discussed in the framework of the variational theory in fibred manifolds. Necessary and sufficient conditions for generators of one-parameter groups of such transformations are derived, completing thus some previous results of A. Trautman on the theory of transformations. 相似文献
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14.
V. Tsurkan St. Plogmann M. Demeter D. Hartmann M. Neumann 《The European Physical Journal B - Condensed Matter and Complex Systems》2000,15(3):401-403
X-ray photoelectron spectroscopy was used to investigate ACr2S4 (, Zn, Mn, Fe, Fe:Cu) and BCr2Se4 (, Cu, Hg, Hg:Cu) single crystals. Well defined splitting of the Cr 2p core level has been found. The local magnetic moments of the Cr ions are responsible for the observed effect.
Received 2 November 1999 相似文献
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Daniella Takács Ildikó Nagy Orsolya Egyed György Hajós 《Journal of organometallic chemistry》2010,695(24):2673-2678
Phenothiazinyldienes obtained from tetrazolopyridinium salts and phenothiazine derivatives were subjected to reduction by borane-dimethyl sulfide in THF. Structure elucidation of the products revealed that one of the olefinic bond underwent reduction and, furthermore, borane addition at the double bond took place to yield derivatives of tetrazolo[5,1-f][1,2]azaborinin as a new fused ring system involving a bridge-head nitrogen atom. The new products have been synthesized and characterized by X-ray analysis, solution and solid-state NMR. 相似文献
17.
Ms. Orsolya Tischler Mr. Balázs Tóth Dr. Zoltán Novák 《Chemical record (New York, N.Y.)》2017,17(2):184-199
This account collects the developments and transformations which avoid the utilization of harsh reaction conditions in the field of palladium catalyzed, ortho‐directed C?H activation of aniline derivatives from the first attempts to up‐to‐date results, including the results of our research laboratory. The discussed functionalizations performed under mild conditions include acylation, olefination, arylation, alkylation, alkoxylation reactions. Beside the optimization studies and the synthetic applications mechanistic investigations are also presented. 相似文献
18.
Karácsony O Akhremitchev BB 《Langmuir : the ACS journal of surfaces and colloids》2011,27(18):11287-11291
Force spectroscopy is a novel tool in physical chemistry and biophysics. This methodology is aimed at providing kinetic parameters of dissociation at a single-molecule level by rupturing molecular bonds subjected to different loading rates. One persistent problem in the implementation of this methodology is a question about the single-bond nature of the rupture events detected in experiments based on atomic force microscopy. Here we address this question by considering the probability that the nearly simultaneous rupture of two molecular bonds might appear as a single bond rupture in the experimental data, complicating the data analysis and contributing to systematic errors in the extracted kinetic parameters. An approximate analytical model predicts that such events might be common in experiments employing soft cantilever force sensors and short tethers to immobilize the interacting molecules. These findings are confirmed by a more elaborate numerical model providing valuable guidelines on performing single-molecule force spectroscopy experiments. 相似文献
19.
Galievsky VA Druzhinin SI Demeter A Kovalenko SA Senyushkina T Mayer P Zachariasse KA 《The journal of physical chemistry. A》2011,115(40):10823-10845
The excited state behavior of the six m,n-dicyano-N,N-dimethylanilines (mnDCDMA) and m,n-dicyano-(N-methyl-N-isopropyl)anilines (mnDCMIA) is discussed as a function of solvent polarity and temperature. The dicyano moiety in these electron donor (D)/acceptor (A) molecules has a considerably larger electron affinity than the benzonitrile subgroup in 4-(dimethylamino)benzonitrile (DMABN). Nevertheless, the fluorescence spectra of the mnDCDMAs and mnDCMIAs in n-hexane all consist of a single emission originating from the locally excited (LE) state, indicating that a reaction from LE to an intramolecular charge transfer (ICT) state does not take place. The calculated energies E(ICT), obtained by employing the reduction potential of the dicyanobenzene subgroups and the oxidation potential of the amino substituents trimethylamine (N(Me)(3)) and isopropyldimethylamine (iPrNMe(2)), are lower than E(LE). The absence of an LE → ICT reaction therefore makes clear that the D and A units in the dicyanoanilines are not electronically decoupled. In the polar solvent acetonitrile (MeCN), dual (LE + ICT) fluorescence is found with 24DCDMA and 34DCDMA, as well as with 24DCMIA, 25DCMIA, and 34DCMIA. For all other mnDCDMAs and mnDCMIAs, only LE emission is observed in MeCN. The ICT/LE fluorescence quantum yield ratio Φ'(ICT)/Φ(LE) in MeCN at 25 °C is larger for 24DCDMA (1.2) than for 34DCDMA (0.35). The replacement of methyl by isopropyl in the amino substituent leads to a considerable increase of Φ'(ICT)/Φ(LE), 8.8 for 24DCMIA and 1.4 for 34DCMIA, showing that the LE ? ICT equilibrium has shifted further toward ICT. The appearance of an ICT reaction with the 2,4- and 3,4-dicyanoanilines is caused by a relatively small energy gap ΔE(S(1),S(2)) between the two lowest excited singlet states as compared with the other m,n-dicyanoanilines, in accordance with the PICT model. The observation that the ICT reaction is more efficient for 24DCMIA and 34DCMIA than for their mnDCDMA counterparts is mainly caused by the fact that iPrNMe(2) is a better electron donor than N(Me)(3): E(D/D(+)) = 0.84 against 1.05 V vs SCE. That ICT also occurs with 25DCMIA, notwithstanding its large ΔE(S(1),S(2)), is due to the substantial amino twist angle θ = 42.6°, which leads to partial electronic decoupling of the D and A subgroups. The dipole moments μ(e)(ICT) range between 18 D for 34DCMIA and 12 D for 25DCMIA, larger than the corresponding μ(e)(LE) of 16 and 11 D. The difference between μ(e)(ICT) and μ(e)(LE) is smaller than with DMABN (17 and 10 D) because of the noncollinear arrangement of the amino and cyano substituents (different dipole moment directions). The dicyanoanilines that do not undergo ICT, have LE dipole moments between 9 and 16 D. From plots of ln(Φ'(ICT)/Φ(LE)) vs 1000/T, the (rather small) ICT reaction enthalpies ΔH could be measured in MeCN: 5.4 kJ/mol (24DCDMA), 4.7 kJ/mol (24DCMIA), and 3.9 kJ/mol (34DCMIA). With the mnDCDMAs and mnDCMIAs only showing LE emission, the fluorescence decays are single exponential, whereas for those undergoing an LE → ICT reaction the LE and ICT picosecond fluorescence decays are double exponential. In MeCN at 25 °C, the decay times τ(2) have values between 1.8 ps for 24DCMIA and 4.6 ps for 34DCMIA at 25 °C. Longer times are observed at lower temperatures. Arrhenius plots of the forward and backward ICT rate constants k(a) and k(d) of 25DCMIA in tetrahydrofuran, obtained from the LE and ICT fluorescence decays, give the activation energies E(a) = 4.5 kJ/mol and E(d) = 11.9 kJ/mol, i.e., ΔH = -7.4 kJ/mol. From femtosecond transient absorption spectra of 24DCDMA and 34DCDMA at 22 °C, ICT reaction times τ(2) = 1/(k(a) + k(d)) of 1.8 and 3.1 ps are determined. By combining these results with the data for the fluorescence decays and Φ'(ICT)/Φ(LE), the values k(a) = 49 × 10(10) s(-1) (24DCDMA) and k(a) = 23 × 10(10) s(-1) (34DCDMA) are calculated. An LE and ICT excited state absorption is present even at a pump/probe delay time of 100 ps, showing that an LE ? ICT equilibrium is established. 相似文献
20.
Kenny B. Lipkowitz David A. Demeter Jo. M. Landwer Carol A. Parish Thomas Darden 《Journal of computational chemistry》1988,9(1):63-66
The multidimensional potential energy surface for a soluble analog of a chiral phase is computed with MM2 and MNDO. Minimum energy conformations are located. The minimum energy reaction pathway between these forms is located, and the templating ability of these phases is described. 相似文献