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31.
Thilo Berkenbusch Andy Ch. Laungani Reinhard Brückner Manfred Keller 《Tetrahedron letters》2004,45(52):9517-9520
4-tert-Butyl-2-cyclohexen-1-one dimerizes in THF solution via its kinetic enolate, leading to di-tert-butylditwistane 8 in up to 36% yield (−78 °C → room temp., protonolysis, flash chromatography). X-ray crystallography shows that 8 incorporates one R and one S enantiomer of the starting ketone; none of the diastereomeric ditwistanes epi-8, epi’-8 or iso-8 was isolated. This means that the formation of 8 proceeds with mutual kinetic resolution and 100% induced diastereoselectivity. 相似文献
32.
Antonio Currao Nantko Feiken Alceo Macchioni Reinhard Nesper Paul S. Pregosin Gerald Trabesinger 《Helvetica chimica acta》1996,79(6):1587-1591
The ligand (6,6′-dimethoxybiphenyl-2,2′-diyl)bis[3,5-di(tert-butyl)phenylphosphine] ( 1 ) forms an unexpectedly stable hydrido-bis-solvento complex of composition [RuH(isopropanol)2( 1 )]BF4, ( 2 ) under the conditions used in the enantioselective hydrogenation of pyrones. The structure of 2 , determined by X-ray diffraction, represents the first well-characterized chiral five-coordinate bis-phosphine ruthenium-hydride complex stable as a solvento complex, and provides a structural link in the enantioselective pyrone hydrogenation cycle catalyzed by [Ru(OAc)2( 1 )]. Using the arene complex [RuH(p-cymene)( 1 )]BF4 ( 3 ), the chiral pocket of coordinated 1 is shown to be relatively rigid, via NMR spectroscopy. This is reflected in restricted rotation about one of the four P–[3,5-di(tert-butyl)phenyl] P? Cipso bonds at room temperature. 相似文献
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Motivated by the concept of maximum entropy methods in signal and image processing, we introduce and discuss a class of ‘directed diffusion equations’ with suitable boundary conditions. The paradigmatic ‘directed diffusion equation’ is The relative entropy $ Sb[f](t): = - \int_\Omega {f(t,x)} \;\ln \;(f(t,x)/b(x))dx $ is rapidly increasing along solution trajectories of (i). This suggests that solving (i) will yield efficient procedures for entropy maximization. We also discuss the asymptotic behavior of solutions of (i)—this is readily done because (i) has a large family of Ljapunov functionals. 相似文献
36.
M. A. Baldwin A. G. Loudon R. E. Dunmur R. Schmutzler I. K. Gregor 《Journal of mass spectrometry : JMS》1977,12(5):275-278
The ionization potentials of a series of N-methyl,N′-R-1,2,4-phosphadiazetidine-3-ones and related compounds have been determined. The nature of the highest occupied orbital of the molecules and the use of empirical rules to rationalize the variations in the ionization potentials are discussed. The changes in the fragmentation patterns are related to the different low ionization potential site(s) in each molecule. The occurrence of various rearrangement ions are discussed on a similar basis. 相似文献
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Gololobov Yu. G. Galkina M. A. Dovgan O. V. Krasnova I. Yu. Petrovskii P. V. Antipin M. Yu. Voronzov I. I. Lyssenko K. A. Schmutzler R. 《Russian Chemical Bulletin》2001,50(2):279-286
The reactions of the zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate with mercuric chloride and aryl isothiocyanates containing Cl atoms in the ortho positions of the benzene ring follow an unusual pathway because this zwitterion represents latent triisopropylphosphine due to the reversibility of the reaction of triisopropylphosphine with ethyl 2-cyanoacrylate. The molecular structures of the adducts of triisopropylphosphine with 2,6-dichloro- and 2,4,6-trichlorophenyl isothiocyanates were confirmed by X-ray diffraction study. Protonation of the adduct of triisopropylphosphine with 2,6-dichlorophenyl isothiocyanate occurred at the nitrogen atom, whereas methylation with methyl trifluoromethanesulfonate afforded an S-methylation product. The results of X-ray diffraction study of the resulting compounds are presented. 相似文献
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Novel Inorganic Ring Systems. 34. Derivatives of the Cyclo-1-thiaIV- and of the Cyclo-1-thia VI-3,4-disila-2,5-diazane Variations of fivemembered “hetero” cyclosilazanes of the type Si2N2El could be enlarged to the systems with El = SO and SO2. They are obtained by the formation principles 4 + 1 and 2 + 3 respectively, according to the equation (1), (4) and (5). The prepared compound are described in their properties and confirmed in their structure (Tables 1–2). 相似文献