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81.
Mechanistic Insights into the Post‐Cyclization Isomerization in Gold‐Catalyzed 7‐exo‐dig‐Hydroarylations
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M. Sc. Daniel Pflästerer Sören Schumacher Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11585-11589
The subsequent double‐bond isomerization in the synthesis of dibenzocycloheptenes and their heteroaromatic analogues was investigated. In the case of biphenyls, a basic additive completely prevented an isomerization to the thermodynamic product. With electron‐rich intramolecular heteroaromatic nucleophiles, the isomerization was still observed, but the kinetic product can be obtained by careful control of the reaction times in most cases. Mechanistic studies demonstrated that a slow isomerization is also possible with the gold catalyst at elevated temperatures, but much faster isomerization rates were observed with acidic additives. An observed initiation period for the gold‐catalyzed isomerization indicates that not the homogenous catalyst, but a decomposition product of it may be the catalytically active species. 相似文献
82.
Helmut Rudolph 《Optimization》2015,64(8):1739-1757
83.
Shestakova P Willem R Vassileva E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(52):14867-14877
(1)H HRMAS NMR spectroscopy is applied to gain insight into the chemical and morphological structure of double-network (DN) hydrogels, prepared from poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) and poly(acrylamide) (PAAm). The method enables one to obtain detailed information at the molecular level about the formation of covalent bonds between the two polymer networks through non-reacted double bonds of the cross-linker N,N'-methylene bis(acrylamide) (MBAA). Evidence to the existence of strong hydrogen-bond interactions based on the N-H group of the PAMPS as a hydrogen-bond donor and the C=O group of the PAAm as a hydrogen-bond acceptor is also provided. These findings clarify the origin of the toughening mechanism and the exceptionally strong mechanical properties of DN gels, further supported by microhardness data. 相似文献
84.
Anger E Rudolph M Shen C Vanthuyne N Toupet L Roussel C Autschbach J Crassous J Réau R 《Journal of the American Chemical Society》2011,133(11):3800-3803
Hetero- and homochiral diastereomeric bis(metallahelicene)s have been synthesized. They possess a rare Pt(III)-Pt(III) scaffold bridged by benzoato ligands. It is shown that heterochiral (P,M)-bis(Pt(III)-[6]helicene) can isomerize into the homochiral (P,P)- and (M,M)-bis(Pt(III)-[6]helicene). A theoretical study shows a unique σ-π conjugation between the two π-helices and the σ-Pt(III)-Pt(III) scaffold that impacts the strong chiroptical properties. 相似文献
85.
Rudolph WW Irmer G 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(5):1483-1492
Aqueous solutions of sodium tribromoacetate (NaCBr3CO2) and its corresponding acid (CBr3COOH) have been studied using Raman and infrared spectroscopy. The spectra of the species in solution were assigned according to symmetry Cs. Characteristic bands of CBr3CO2-(aq) and the tribromoacetic acid, CBr3COOH(aq), are discussed. For the hydrated anion, the CO2 group, the symmetric CO2 stretching mode at 1332 cm(-1) and the asymmetric stretching mode at 1651 cm(-1) are characteristic while the CO mode at 1730 cm(-1) is characteristic for the spectra of the acid. The stretching mode, νC-C at 912cm(-1) for CBr3CO2-(aq) is 10 cm(-1) lower in the anion compared with that of the acid. These characteristic modes are compared to those in acetate, CH3CO2-(aq). Coupling of the modes are fairly extensive and therefore DFT calculations have been carried out in order to compare the measured spectra with the calculated ones. The geometrical parameters such as bond length and bond angles of the tribromoacetate, and tribromoacetic acid have been obtained and may be compared with the ones published for other acetates and their conjugated acids. CBr3COOH(aq) is a moderately strong acid and the pKa value derived from quantitative Raman measurements is equal to -0.23 at 23°C. The deuterated acid CBr3COOD in heavy water has been measured as well and the assignments were given. 相似文献
86.
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88.
L. Corradi S. J. Skorka U. Lenz K. E. G. Löbner P. R. Pascholati U. Quade K. Rudolph W. Schomburg M. Steinmayer H. G. Thies G. Montagnoli D. R. Napoli A. M. Stefanini A. Tivelli S. Beghini F. Scarlassara C. Signorini F. Soramel 《Zeitschrift für Physik A Hadrons and Nuclei》1990,335(1):55-72
Double differential cross sections of all prominent transfer channels have been measured in the systems33S +99,91,92Zr at two energies close to the nominal Coulomb barrier. In addition the fusion excitation functions of these systems have been measured below and around the barrier. The angular- andQ-distributions of the most important transfer reactions have been analysed in the framework of a simple semiclassical formalism. Particularly the two-nucleon transfer angular distributions exhibit strong multi step coupling effects which manifest themselves in reduced cross sections at large angles corresponding to close distances. From the angular distributions at forward angles, where a single step character of the transfer reaction can be assumed, approximate form factors have been extracted employing a first order perturbation theory. Within the uncertainties of a schematic coupled channels calculation the isotopic differences of the sub-barrier fusion enhancement can be understood on the basis of the isotopic differences of the transfer form factors andQ-values. 相似文献
89.
90.
L-L. Andersson D. Rudolph J. Ekman C. Fahlander E. K. Johansson R. du Rietz C. J. Gross P. A. Hausladen D. C. Radford G. Hammond 《The European Physical Journal A - Hadrons and Nuclei》2006,30(2):381-390
The 61
30Zn31 isotope has been produced at the Oak Ridge National Laboratory in the fusion-evaporation reaction 40Ca(24Mg, 2pn)61Zn at 104MeV. The experimental set-up allowed γ-rays to be detected in the CLARION Ge detector array in coincidence with the
detection of recoiling nuclei in the focal plane at the end of the recoil mass spectrometer. This provides a unique identification
of γ-rays belonging to 61Zn. The excited states have been explored by means of recoil- γγ coincidences, and the resulting decay scheme comprises almost
70 transitions. The data reveal numerous non-yrast states and suggest a revised spin and parity assignment for a previously
observed superdeformed band. The resulting decay scheme is compared to predictions from different sets of large-scale shell
model calculations. 相似文献