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1.
Jónsson S Odille FG Norrby PO Wärnmark K 《Chemical communications (Cambridge, England)》2005,(4):549-551
A dynamic supramolecular system involving hydrogen bonding between a Mn(III) salen catalyst and a Zn(II) porphyrin receptor exhibits selectivity for pyridine appended cis-beta-substituted styrene derivatives over phenyl appended derivatives in a catalytic epoxidation reaction. 相似文献
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A. Bergier H. Gennow S. Nilsson J. Norrby W. Evans J. R. Fry P. Mason H. Muirhead H. Fenker J. Marraffino S. Reucroft C. Roos M. S. Webster 《Zeitschrift fur Physik C Particles and Fields》1980,5(4):265-274
We present data on \(\bar pn\) and π? n collisions obtained from an exposure of the 30′' FNAL deuterium filled bubble chamber to a mixed \({{\bar p} \mathord{\left/ {\vphantom {{\bar p} {\pi ^ - }}} \right. \kern-0em} {\pi ^ - }}\) beam with a momentum of 100 GeV/c. We find that in 17±2% of the collisions with the antiproton there is an interaction on the spectator while for the collisions with π? mesons the corresponding number is 15±2%. The \(\bar pn\) and π? n multiplicity distributions have average charged multiplicities of 6.46±0.07 and 6.53±0.08 respectively. The average multiplicities for both types of interactions are slightly smaller than those for the corresponding reactions on hydrogen by an amount that is the same as observed at other energies. As an estimate of \(\bar pn\) annihilation we have calculated the difference \(\sigma _n (\bar pn) - \sigma _n (pn)\) for each prong numbern. We find an average multiplicity of 9±1, a value close to that for \(\bar pp\) annihilation at the same energy. combining our data with lower energy \(\bar pn\) annihilation data, we observe that the average negative multiplicity is systematically larger than that for \(\bar pp\) annihilation similar to the difference between neutron and proton target data with other beam projectiles. 相似文献
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Linde C Koliaï N Norrby PO Akermark B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2568-2573
The substrate electronic effects on the selectivity in the catalytic epoxidation of para-substituted cis stilbenes 2a-i were investigated by using (R,R)-[N,N'-bis(3,5-di-tBu-salicylidene)-1,2-cyclohexanediamine]manganese(III) chloride 1 in benzene as the catalyst with iodosobenzene as the terminal oxidant. A Hammett study of the selectivity results reveals a stronger electrophilic character than previously assumed in the (salen)Mn-catalyzed reaction. In general, the best correlations with the experimental values were obtained by using the Hammett sigma + values, which gave rho = -1.37 for the rate of cis-epoxide formation and rho = -0.43 for the rate of the stepwise process leading to the corresponding trans product. The reaction involves two separate pathways as indicated also by the competitive breakdown of the intermediate on the path to trans epoxide for methoxy-substituted substrates. The asynchronicity in the concerted pathway leading to cis epoxide is apparent for 4-methoxy-4'-nitrostilbene, which yields cis epoxide with 75% ee entirely as a result of electronic effects. 相似文献
4.
Rasmussen T Jensen JF Ostergaard N Tanner D Ziegler T Norrby PO 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(1):177-184
The selectivity-determining step in enantioselective copper-catalyzed cyclopropanation with diazo compounds has been studied by experimental and computational methods. The addition of the very reactive metallacarbene intermediate in an early transition state to the substrate alkene is concerted but strongly asynchronous, with substantial cationic character on one alkene carbon in the neighborhood of the transition state. Evidence from isotope effects and Hammett studies supports the nature of the transition state. Formation of a metallacyclobutane intermediate by a [2+2] addition is kinetically disfavored. Ligand-substrate interactions influencing the enantio- and diastereoselectivity have been identified, and the preferred orientation of the alkene substrate during the addition is suggested. 相似文献
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All methionine aminopeptidases exhibit the same conserved metal binding site. The structure of this site with either Co2+ions or Zn2+ions was investigated using density functional theory. The calculations showed that the structure of the site was not influenced by the identity of the metal ions. This was the case for both of the systems studied; one based on the X-ray structure of the human methionine aminopeptidase type 2 (hMetAP-2) and the other based on the X-ray structure of the E. colimethionine aminopeptidase type 1 (eMetAP-1). Another important structural issue is the identity of the bridging oxygen, which is part of either a water molecule or a hydroxide ion. Within the site of hMetAP-2 the results strongly indicate that a hydroxide ion bridges the metal ions. By contrast, the nature of the oxygen bridging the metal ions within the metal binding site of eMetAP-1 cannot be determined based on the results here, due to the similar structural results obtained with a bridging water molecule and a bridging hydroxide ion. 相似文献
6.
Pedersen TM Hansen EL Kane J Rein T Helquist P Norrby PO Tanner D 《Journal of the American Chemical Society》2001,123(40):9738-9742
A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different alpha-oxygen-substituted, racemic aldehydes were initially transformed by asymmetric HWE reactions into mixtures of two major alpha,beta-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution reactions with carbon, nitrogen, and oxygen nucleophiles. In this latter step, the respective (E) and (Z) alkene substrate isomers were observed to react with opposite stereospecificity: the (E) alkene reacted with retention and the (Z) alkene with inversion of stereochemistry with respect to both the allylic stereocenter and the alkene geometry. Thus, a single gamma-substituted ester was obtained as the overall product, in high isomeric purity. The method was applied to a synthesis of a subunit of the iejimalides, a group of cytotoxic macrolides. 相似文献
7.
The Tamao oxidation of alkoxysilanes was investigated computationally to determine the role of fluoride, a key additive, in this reaction. A sequence of fluoride equilibria as well as possible transition states, mediated by basic and neutral peroxide, respectively, were examined, and a potential energy surface was calculated which was consistent with the typical synthetic methods required for the conversion of alkoxysilanes to alcohols. 相似文献
8.
S. Yu. Torilov K. A. Gridnev V. I. Zherebchevsky M. Brenner L. I. Vinogradov V. Z. Goldberg T. V. Korovitskaya T. Lönnroth N. A. Maltsev M. Mutterer B. G. Novatskii M. Norrby J. M. K. Slotte Yu. G. Sobolev W. H. Trzaska G. P. Tyurin S. V. Khlebnikov 《JETP Letters》2011,94(1):6-10
High-spin states of the 22Ne nucleus in the excitation energy range of 15–30 MeV have been studied. The angular correlation method has been used to determine the spins of excited states. A number of new states with high angular momenta—20.0 MeV (9?), 20.7 MeV (11?), 21.6 MeV (9?), 22.2 MeV (12+), and 25.0 MeV (9?)—have been revealed. They are intensely populated in the reaction 14C(12C, α1)22Ne* → α2 + 18O and correspond to the rotational bands of various structures. 相似文献
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