@article{BringmannMutanyattaComarMaksimenkaetal.2008, author = {Bringmann, Gerhard and Mutanyatta-Comar, Joan and Maksimenka, Katja and Wanjohi, John M. and Heydenreich, Matthias and Brun, Reto and M{\"u}ller, Werner E. G. and Peter, Martin G. and Midiwo, Jacob O. and Yenesew, Abiy}, title = {Joziknipholones A and B : the first dimeric phenylanthraquinones, from the roots of Bulbine frutescens}, issn = {0947-6539}, year = {2008}, abstract = {From the roots of the African plant Bulbine frutescens (Asphodelaceae), two unprecedented novel dimeric phenylanthraquinones, named joziknipholones A and B, possessing axial and centrochirality, were isolated, together with six known compounds. Structural elucidation of the new metabolites was achieved by spectroscopic and chiroptical methods, by reductive cleavage of the central bond between the monomeric phenylanthraquinone and -anthrone portions with sodium dithionite, and by quantum chemical CD calculations. Based on the recently revised absolute axial configuration of the parent phenylanthraquinones, knipholone and knipholone anthrone, the new dimers were attributed to possess the P- configuration (i.e., with the acetyl portions below the anthraquinone plane) at both axes in the case of joziknipholone A, whereas in joziknipholone B, the knipholone part was found to be M-configured. Joziknipholones A and B are active against the chloroquine resistant strain K1 of the malaria pathogen, Plasmodium falciparum, and show moderate activity against murine leukemic lymphoma L5178y cells.}, language = {en} } @article{HaebelHejaziFrohbergetal.2008, author = {Haebel, Sophie and Hejazi, Mahdi and Frohberg, Claus and Heydenreich, Matthias and Ritte, Gerhard}, title = {Mass spectrometric quantification of the relative amounts of C6 and C3 position phosphorylated glucosyl residues in starch}, issn = {0003-2697}, year = {2008}, abstract = {The quantification of phosphate bound to the C6 and C3 positions of glucose residues in starch has received increasing interest since the importance of starch phosphorylation for plant metabolism was discovered. The method described here is based on the observation that the isobaric compounds glucose-6-phosphate (Glc6P) and glucose-3- phosphate (Glc3P) exhibit significantly different fragmentation patterns in negative ion electrospray tandem mass spectrometry (MS/MS). A simple experiment involving collision-induced dissociation (CID) MS2 spectra of the sample and the two reference substances Glc3P and Glc6P permitted the quantification of the relative amounts of the two compounds in monosaccharide mixtures generated by acid hydrolysis of starch. The method was tested on well-characterized potato tuber starch. The results are consistent with those obtained by NMR analysis. In contrast to NMR, however, the presented method is fast and can be performed on less than 1 mg of starch. Starch samples of other origins exhibiting a variety of phosphorylation degrees were analyzed to assess the sensitivity and robustness of the method.}, language = {en} } @article{HeydenreichKochSzatmarietal.2008, author = {Heydenreich, Matthias and Koch, Andreas and Szatm{\´a}ri, Istv{\´a}n and Fulop, Ferenc and Kleinpeter, Erich}, title = {Synthesis and conformational analysis of naphth[1,2-e][1,3]oxazino[4,3-a][1,3]isoquinoline and naphth[2,1- e][1,3]oxazino[4,3-a]isoquinoline derivatives}, doi = {10.1016/j.tet.2008.05.025}, year = {2008}, abstract = {Through the cyclization of 1-(;-hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinoline and 1-(;- hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinoline with formaldehyde, phosgene, p-nitrobenzaldehyde or p-chlorophenyl isothiocyanate, 8-substituted 10,11-dihydro-8H,15bH-naphth[1,2-e][1,3]oxazino[4,3-a]isoquinolines (3 and 4) and 10,11- dihydro-8H,15bH-naphth[2,1-e][1,3]oxazino[4,3-a]isoquinolines (15 and 16) were prepared. Conformational analysis of both the piperidine and the 1,3-oxazine moieties of these heterocycles by NMR spectroscopy and an accompanying theoretical study revealed that these two conformationally flexible six-membered ring moieties prefer twisted chair conformers.}, language = {en} } @article{SchusterKochHeydenreichetal.2008, author = {Schuster, Ildik{\´o} and Koch, Andreas and Heydenreich, Matthias and Kleinpeter, Erich and Forr{\´o}, Enik{\"o} and L{\´a}z{\´a}r, L{\´a}szl{\´o} and Sillanp{\"a}{\"a}, Reijo and Fulop, Ferenc}, title = {Synthesis and Conformational Analysis of Tetrahydroisoquinoline-Fused 1,3,2-Oxazaphospholidines and 1,2,3- Oxathiazolidines}, year = {2008}, abstract = {The cyclizations of tetrahydroisoquinoline 1,2-amino alcohols with phenylphosphonic dichloride, bis(2- chloroethyl)phosphoramidic dichloride, thionyl chloride and sulfuryl chloride were utilized to synthesize 1,5,6,10b- tetrahydro-1,3,2-oxazaphospholo[4,3-a]isoquinolines (2, 3), 1,5,10,10a-tetrahydro-1,3,2-oxazaphospholo[3,4- b]isoquinolines (8, 9), 1,5,6,10b-tetrahydro-1,2,3-oxathiazolo[4,3-a]isoquinolines (4-6) anda 1,5,10,10a-tetrahydro- 1,2,3-oxathiazolo[3,4-b]isoquinoline (11), which are the first representatives of these ring systems. NMR spectroscopic analysis revealed the existence of conformational equilibria that are fast on the NMR timescale. Theoretical DFT calculations pointed to the participation of generally two preferred conformers in the conformational equilibria; the positions of the equilibria were indicated by the experimental NMR spectroscopic parameters, and they are in good agreement with the theoretically calculated energy differences of the participating conformers. For two compounds, which could be not isolated (10, 12), both the preferred conformers and the stereochemistry could be concluded from the DFT calculation results.}, language = {en} }