TY - JOUR A1 - Gumula, Ivan A1 - Heydenreich, Matthias A1 - Derese, Solomon A1 - Ndiege, Isaiah O. A1 - Yenesew, Abiy T1 - Four isoflavanones from the stem bark of Platycelphium voense JF - Phytochemistry letters N2 - From the stem bark of Platycelphium voense (Leguminosae) four new isoflavanones were isolated and characterized as (S)-5,7-dihydroxy-2 ',4 '-dimethoxy-3 '-(3 ''-methylbut-2 ''-enyl)-isoflavanone (trivial name platyisoflavanone A), (+)-5,7,2 '-trihydroxy-4 '-methoxy-3 '-(3 ''-methylbut-2 ''-enyl)-isoflavanone (platyisoflavanone B), 5,7-dihydroxy-4 '-methoxy-2 ''-(2 '''-hydroxyisopropyl)-dihydrofurano-[4 '',5 '':3 ',2 ']-isoflavanone (platyisoflavanone C) and 5,7,2 ',3 ''-tetrahydroxy-2 '',2 ''-dimethyldihydropyrano-[5 '',6 '':3 ',4 ']-isoflavanone (platyisoflavanone D). In addition, the known isoflavanones, sophoraisoflavanone A and glyasperin F; the isoflavone, formononetin; two flavones, kumatakenin and isokaempferide; as well as two triterpenes, betulin and beta-amyrin were identified. The structures were elucidated on the basis of spectroscopic evidence. Platyisoflavanone A showed antibacterial activity against Mycobacterium tuberculosis in the microplate alamar blue assay (MABA) with MIC = 23.7 mu M, but also showed cytotoxicity (IC50 = 21.1 mu M) in the vero cell test. KW - Platycelphium voense KW - Stem bark KW - Leguminosae KW - Isoflavanones KW - Platyisoflavanone KW - Mycobacterium tuberculosis Y1 - 2012 U6 - https://doi.org/10.1016/j.phytol.2011.11.012 SN - 1874-3900 VL - 5 IS - 1 SP - 150 EP - 154 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Heydenreich, Matthias A1 - Koch, Andreas A1 - Linker, Torsten T1 - Synthesis and NMR spectroscopic conformational analysis of esters of 4-hydroxy-cyclohexanone-the more polar the molecule the more stable the axial conformer JF - Tetrahedron N2 - The esters of 4-hydroxy-cyclohexanone and a series of carboxylic acids R-COOH with R of different electronic and steric influence (R=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, and CBr3) were synthesized and the conformational equilibria studied by H-1 and C-13 NMR spectroscopy at 103 K and at 295 K, respectively. The geometry of optimized structures of the axial 'equatorial chair conformers was computed at the ab initio MO and DFT levels of theory. Only one preferred conformation was obtained for the axial and the equatorial conformer as well. When comparing the conformational equilibria of the cyclohexanone esters with those of the corresponding cyclohexyl esters a certain polarity contribution of the cyclohexanone framework was revealed, which is independent of the substituent effects and increases the stability of the axial conformers by a constant amount. KW - 4-Substituted cyclohexanones KW - Conformational analysis KW - Dynamic NMR KW - Simulation of H-1 NMR spectra KW - Quantum chemical calculations KW - ALTONA equation Y1 - 2012 U6 - https://doi.org/10.1016/j.tet.2012.01.022 SN - 0040-4020 VL - 68 IS - 10 SP - 2363 EP - 2373 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Träger, Juliane A1 - Klamroth, Tillmann A1 - Kelling, Alexandra A1 - Lubahn, Susanne A1 - Cleve, Ernst A1 - Mickler, Wulfhard A1 - Heydenreich, Matthias A1 - Müller, Holger A1 - Holdt, Hans-Jürgen T1 - Complexation of Palladium(II) with unsaturated Dithioethers a systematic development of highly selective ligands for solvent extraction JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - There is a demand for new and robust PdII extractants due to growing recycling rates. Chelating dithioethers are promising substances for solvent extraction as they form stable square-planar complexes with PdII. We have modified unsaturated dithioethers, which are known to coordinate PdII, and adapted them to the requirements of industrial practice. The ligands are analogues of 1,2-dithioethene with varying electron-withdrawing backbones and polar end-groups. The crystal structures of several ligands and their palladium complexes were determined as well as their electro- and photochemical properties, complex stability and behaviour in solution. Solvent extraction experiments showed the superiority of some of our ligands over conventionally used extractants in terms of their very fast reaction rates. With highly selective 1,2-bis(2-methoxyethylthio)benzene (4) it is possible to extract PdII from a highly acidic medium in the presence of other base and palladium-group metals. KW - Renewable resources KW - Palladium KW - Chelates KW - Ligand design KW - S li-gands Y1 - 2012 U6 - https://doi.org/10.1002/ejic.201101406 SN - 1434-1948 IS - 14 SP - 2341 EP - 2352 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Csütörtöki, Renata A1 - Szatmari, Istvan A1 - Koch, Andreas A1 - Heydenreich, Matthias A1 - Kleinpeter, Erich A1 - Fulop, Ferenc T1 - Syntheses and conformational analyses of new naphth[1,2-e][1,3]oxazino[3,2-c] quinazolin-13-ones JF - Tetrahedron N2 - The syntheses of naphth[1,2-e][1,3]oxazino[3,2-c]quinazolin-13-one derivatives (3a-f) were achieved by the solvent-free heating of benzyloxycarbonyl-protected intermediates (2a-f) with MeONa. For intermediates 2a-f, prepared by the reactions of substituted aminonaphthols with benzyl N-(2-formylphenyl)carbamate, not only the expected trans ring form B and chain form A(1), but also the rearranged chain form A(2) as a new tautomer were detected in DMSO at room temperature. The quantity of A(2) in the tautomeric mixture was changed with time. Conformational analyses of the target heterocycles 3a-f by NMR spectroscopy and accompanying theoretical calculations at the DFT level of theory revealed that the oxazine ring preferred a twisted chair conformation and the quinazolone ring was planar. Besides the conformations, both the configurations at C-7a and C-15 and the preferred rotamers of the 1-naphthyl substituent at C-15 were assigned, which allowed evaluation of the aryl substituent-dependent steric hindrance in this part of the molecules. Configurational assignments were corroborated by quantifying the ring current effect of 15-aryl in terms of spatial NICS. KW - Naphthoxazinoquinazolinones KW - Aminonaphthols KW - NMR spectroscopy KW - Conformational analysis KW - Theoretical calculations KW - Ring current effect Y1 - 2012 U6 - https://doi.org/10.1016/j.tet.2012.04.026 SN - 0040-4020 VL - 68 IS - 24 SP - 4600 EP - 4608 PB - Elsevier CY - Oxford ER - TY - CHAP A1 - Machumi, F. A1 - Yenesew, Abiy A1 - Midiwo, J. O. A1 - Heydenreich, Matthias A1 - Kleinpeter, Erich A1 - Khan, S. A1 - Tekwani, B. L. A1 - Walker, L. A. A1 - Muhammad, I T1 - Antiparasitic and anticancer carvotacetone derivatives from Sphaeranthus bullatus T2 - Planta medica : journal of medicinal plant and natural product research Y1 - 2012 SN - 0032-0943 VL - 78 IS - 11 SP - 1201 EP - 1202 PB - Thieme CY - Stuttgart ER - TY - JOUR A1 - Machumi, Francis A1 - Yenesew, Abiy A1 - Midiwo, Jacob O. A1 - Heydenreich, Matthias A1 - Kleinpeter, Erich A1 - Tekwani, Babu L. A1 - Khan, Shabana I. A1 - Walker, Larry A. A1 - Muhammad, Ilias T1 - Antiparasitic and anticancer carvotacetone derivatives of Sphaeranthus bullatus JF - Natural product communications : an international journal for communications and reviews N2 - The CH2Cl2-MeOH (1:1) extract of the aerial parts of Sphaeranthus bullatus, an annual herb native to tropical East Africa, showed activity against chloroquine sensitive D6 (IC50 9.7 mu g/mL) and chloroquine resistant W2 (IC50 15.0 mu g/mL) strains of Plasmodium falciparum. Seventeen secondary metabolites were isolated from the extract through conventional chromatographic techniques and identified using various spectroscopic methods. The compounds were evaluated for their in vitro antiplasmodial, antileishmanial and anticancer activities revealing activity of four carvotacetone derivatives, namely 3-acetoxy-7-hydroxy-5-tigloyloxycarvotacetone (1) 3,7-dihydroxy-5-tigloyloxycarvotacetone (2), 3-acetoxy-5,7-dihydroxycarvotacetone (3) and 3,5,7-trihydroxycarvotacetone (4); with antiplasmodial IC50 values of 1.40, 0.79, 0.60 and 3.40 mu g/mL, respectively, against chloroquine sensitive D6 strains of P. falciparum; antiplasmodial activity of IC50 2.00, 0.90, 0.68 and 2.80 mu g/mL respectively, against chloroquine resistant W2 strains of P. falciparum, antileishmanial IC50, values of 0.70, 3.00, 0.70 and 17.00 mu g/mL, respectively, against the parasite L. donovanii promastigotes, and anticancer activity against human SK-MEL, KB, BT-549 and SK-OV-3 tumor cells, with IC50 values between <1.1 - 5.3 mu g/mL, for 1-3. In addition, cytotoxic effects of the active compounds were evaluated against monkey kidney fibroblasts (VERO) and pig kidney epithelial cells (LLC-PK11). The structures of carvotacetone derivatives were determined by ID and 2D NMR spectroscopy; the absolute stereochemical configuration of 3-acetoxy-7-hydroxy-5-tigloyloxycarvotacetone (I) was determined as 3R, 4R, 5S by circular dichroism, specific rotation, H-1 NMR and 2D NMR ROESY and NOESY experiments. KW - Sphaeranthus bullatus KW - Asteraceae KW - Antiplasmodial KW - Antileishmanial KW - Anticancer KW - Carvotacetones Y1 - 2012 SN - 1934-578X VL - 7 IS - 9 SP - 1123 EP - 1126 PB - NPC CY - Westerville ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Heydenreich, Matthias A1 - Koch, Andreas A1 - Linker, Torsten T1 - Synthesis and NMR spectroscopic conformational analysis of esters of 4-hydroxy-cyclohexanone-the more polar the molecule the more stable the axial conformer N2 - The esters of 4-hydroxy-cyclohexanone and a series of carboxylic acids R-COOH with R of different electronic and steric influence (R=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, and CBr3) were synthesized and the conformational equilibria studied by 1H and 13C NMR spectroscopy at 103 K and at 295 K, respectively. The geometry of optimized structures of the axial/equatorial chair conformers was computed at the ab initio MO and DFT levels of theory. Only one preferred conformation was obtained for the axial and the equatorial conformer as well. When comparing the conformational equilibria of the cyclohexanone esters with those of the corresponding cyclohexyl esters a certain polarity contribution of the cyclohexanone framework was revealed, which is independent of the substituent effects and increases the stability of the axial conformers by a constant amount. Y1 - 2012 SN - 0040-4020 ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Csütörtöki, Renáta A1 - Szatmári, István A1 - Heydenreich, Matthias A1 - Koch, Andreas A1 - Starke, Ines A1 - Fulop, Ferenc T1 - Novel piperidine-fused benzoxazino- and quinazolinonaphthoxazines-synthesis and conformational study N2 - The reactions of 1-(amino(2-hydroxyphenyl)methyl)-2-naphthol (3) and 1-(amino(2-aminophenyl)methyl)-2-naphthol (6) with glutardialdehyde resulted in the formation of piperidine-fused benzoxazinonaphthoxazine 4 and quinazolinonaphthoxazine 7, respectively, both in diastereopure form. The full conformational search protocols of 4 and 7 were successfully carried out by NMR spectroscopy and accompanying molecular modelling; the global minimum-energy conformers of all diastereomers were computed, and the assignments of the most stable stereoisomers, Gtct1 for 4 and Gtct1 for 7, were corroborated by spatial NOE information relating to the H7a-H10a-H15b and H,H coupling patterns of the protons in the flexible part of the piperidine moiety. Additionally, mass spectrometric fragmentation was investigated in collision-induced dissociation experiments. The elemental compositions of the ions were determined by accurate mass measurements. Y1 - 2012 SN - 0040-4020 ER -