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51.
52.
In the course of our investigations on the synthesis of enantiomerically pure anthracycline antibiotics by incorporation of chiral building blocks we prepared the O-methyl 3-deoxy-2-C-ethylribopyranoside 1.1 The further synthetic plan required the conversion of 1 to the dithioacetal 2 followed by glycol cleavage to a partially protected 1,4-dialdehyde for coupling experiments to leucoquinizarine in a Marschalk reaction. However, the reaction sequence failed1 and optically active rhodomycinone had to be synthezised in a different way.2 A reinvestigation of the synthesis revealed that the thioacetalization of 1 using the acidic conditions recommended by Corey et al.3 did not yield the usual open chain dithioacetal 2 but rather three new unexpected products. The less polar fraction was identified by 1H and 13C NMR as tetrahydrofuran derivative 3a with the dithiane ring in a ß-orientation. The solid polar fraction (12%) consisted of a nonseparable 1:2.2 mixture of the epimeric deoxygenation products 4/5. 相似文献
53.
Manfred Regitz Wolfgang Rösch Thomas Allspach Ulrich Annen Karsten Blatter Jürgen Fink 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):479-482
Abstract The syntheses of phospholes (7, [3+2]-cycloaddition), bicyclophosphaalkenes (17, [4+2]-cycloaddition), and phosphabenzenes (15, [4+2]-cycloaddition followed by an extrusion process) starting from the phosphaalkynes (4) are described. The 2–Dewar phosphabenzene 18, obtained from the cyclobutadiene 21 and 4 (R =tBu), is the starting material for the synthesis of the valency isomers 19, 20, 22, and 23. 相似文献
54.
Treatment of the 1,6‐anhydrosugar epoxide 5 with a cyano‐Gilman cuprate [(CuCN (6 eq.), MeLi (12 eq.)] surprisingly led to the open chain rearranged (2S,3R)‐1,2‐dihydroxy‐3,6‐dimethylheptan‐4‐one (7), structurally confirmed by conversion to the corresponding diacetate 8. Another unusual reaction was found by hydrogenation of the 2‐tosyl‐1‐bromosugar 11, leading in one operation to the twofold deoxygenated chiral pyran derivative 14. This procedure might prove to be useful in the rapid deoxygenation of sugar derivatives. 相似文献
55.
Olaf Heitzsch Karsten Gloe Alfréd Sabela Jiří Koryta Edwin Weber 《Journal of inclusion phenomena and macrocyclic chemistry》1992,13(4):311-319
The complex forming properties with alkali metal and ammonium ions of a series of oligo benzo-condensed 18-crown-6 ethers1–8 having a different gradation of lipophilicity and of molecular rigidity are investigated by voltammetry at the interface of two immiscible electrolyte solutions (ITIES) and by a liquid-liquid extraction technique. The experimental results obtained in the two phase system H2O/nitrobenzene are discussed in relation to the structure of the crown and the cation type. The stability constants for the 1 : 1 complexes of Na+, K+, Rb+, Cs+ and NH
4
+
in nitrobenzene have been determined and compared with the extraction constants for the 1: 1 complexes of Na+ and K+ and for the 1 : 1 and 1 : 2 complexes of Cs+, showing the effect of oligo benzo condensation for the 18-crown-6 system. 相似文献
56.
57.
Benjamin Schmidt Benjamin Schrder Karsten Sonnenberg Simon Steinhauer Sebastian Riedel 《Angewandte Chemie (International ed. in English)》2019,58(30):10340-10344
Pseudohalogens are defined as molecular entities that resemble the halogens in their chemistry. While our understanding of polyhalogen chemistry has increased over the last years, research on polypseudohalogen compounds is lacking. The pseudohalogen BrCN possesses a highly pronounced σ‐hole at the bromine side of the molecule, inducing strong halogen bonding. This allows the synthesis and characterization of new polypseudohalogen anions, as shown by the single‐crystal X‐ray diffraction of [PNP][Br(BrCN)] and [PNP][Br(BrCN)3]. Both the nearly linear anion [Br(BrCN)]? and the distorted pyramidal anion [Br(BrCN)3]? were characterized by Raman spectroscopy and quantum‐chemical calculations. The behavior of the polypseudohalogen compounds in solution and as room‐temperature ionic liquids (RT‐ILs) using the [NBu4]+ cation was studied by 13C and 15N NMR spectroscopy. These types of ILs are capable of dissolving elemental gold and offer themselves as promising compounds in metal recycling. 相似文献
58.
A method for semi-automatic background estimation in energy-dispersive x-ray fluorescence spectra is outlined. Two cubic splines were investigated and the spline called the Butland interpolant was chosen for further investigation. Prior to the calculation of the spline, peak regions are set up, and suitable knots are defined outside the peak regions. To set up the peak regions, an automatic peak-search routine and a calibration equation are used. For a given peak, the latter relates the full width at half maximum (FWHM) to the peak centre. In turn, the size of the peak regions are defined by the FWHM multiplied by a constant given by the user. The method was tested on several types of spectra. It was found that the optimal size of the peak region decreased with increasing peak density. Reproducibility tests showed that the standard deviation of the summation of counts within a peak region and after background subtraction was less than would be expected from the counting statistics. 相似文献
59.
More than a dozen stationary points on the potential energy surface for the 1:1 glycine zwitterion—water complex have been investigated at Hartree-Fock or MP2 levels of theory with basis sets ranging from split valence (4-31G) to split valence plus polarization and diffuse function (6–31 + + G**) quality. Only one true minimum (GLYZWM, C1 symmetry) could be located on the potential energy surface. GLYZWM features a bridged water molecule acting as both a hydrogen bond acceptor and donor with the NH3− and CO2− units of the glycine zwitterion. The total hydrogen bond energy in GLYZWM is computed as 16 kcal/mol (MP2/6–31 ++ G** // 6–31 ++ G**, including corrections for basis set superpositions errors). The computed vibrational frequencies and normal mode forms of the GLYZWM complex resemble in many cases experimental assignments made for the glycine zwitterion in bulk water on the basis of Raman spectroscopy. © 1996 by John Wiley & Sons, Inc. 相似文献
60.
Inside Cover: Synthesis of an All‐Ferric Cuboidal Iron–Sulfur Cluster [FeIII4S4(SAr)4] (Angew. Chem. Int. Ed. 36/2018) 下载免费PDF全文