Formation of an organometallic ladderane derivative by dynamic topochemical reaction control.
Explore the source record for details and available documents.
Biomedical subjects
Publications and source records attributed to Klaus Bergander.
Explore the source record for details and available documents.
The four organoaluminium ketoximates [(2,4-dimethylpentane-3-one oximato)AlMe(2)](2) (1), (meso)-[(norcamphor oximato)AlMe(2)](2) (2), {[(R,R)-camphor oximato]AlMe(2)}(3) (3) and {[(R,S)-fenchone oximato]AlMe(2)}(2) (4) have been prepared by the reactions of the corresponding oximes with trimethylaluminium. All compounds have been fully characterized by means of IR, mass and multi-nuclear NMR spectroscopy ((1)H, (13)C, (27)Al) and by elemental analyses. The crystal structures of three of these compounds (2, 3 and 4) were determined, revealing the aggregation motif of organometallic group 13 oximates to vary from the hitherto predominant six-membered dimeric M(2)N(2)O(2) array to others (six-membered M(3)O(3) core ring in the case of the camphor derivative; five-membered M(2)NO(2) core ring in the case of the fenchone derivative) so far only found e.g. in hydroxylamino complexes of group 13 metals. Furthermore, complexes 3 and 4 exhibit an unusual behaviour in solution, as indicated by upfield-shifted additional signals in their (27)Al NMR spectra, pointing at aluminium atoms in penta- or hexacoordination, respectively.
The 1-thio-eta2-alkyne-complex [Tp'(CO)2W(BnSCCS)][Tp'= hydrotris(3,5-dimethylpyrazolyl)borate; Bn = benzyl], which was obtained by reductive removal of the benzyl group at the alkyne complex [Tp'(CO)2W(BnSCCSBn)]PF(6), has been established as a ligand in a combined organometallic/Werner type heterobimetallic complex with Cu(I).
Comparative enantioseparations were performed with three neutral cyclodextrins (CDs) in capillary electrophoresis (CE). In particular, native beta-CD was compared with single component heptakis(2,3-di-O-acetyl)-beta-CD (HDA-beta-CD) and randomly acetylated beta-CD (Ac-beta-CD) with the emphasis on the enantiomer migration order. The opposite affinity of the enantiomers of several chiral analytes was observed towards native beta-CD and its acetylated derivatives. The enantiomer affinity pattern of some chiral analytes was also opposite towards the two acetylated derivatives of beta-CD. In the case of the chiral drug clenbuterol (CL) an attempt was made to evaluate the possible structural reasons of the affinity reversal using one- and two-dimensional as well as transverse rotating frame nuclear Overhauser effect spectroscopy (ROESY). Significant differences were observed between the structure of the CL complexes with beta-CD and HDA-beta-CD.
Enantioseparation of glutethimide (GT) and its 5-hydroxy metabolite (5-OH-GT) has been studied with several charged cyclodextrin (CD) derivatives. The emphasis was made on the enantiomer migration order of GT and simultaneous enantioseparation of GT and 5-OH-GT. The possible structural differences of GT complexes with three different single isomer charged CD derivatives were studied using one-dimensional rotating frame nuclear Overhauser and exchange spectroscopy (1-D ROESY).
Twenty-three cationic chiral analytes were resolved in capillary electrophoresis using native beta-cyclodextrin and single isomer heptakis-(2-O-methyl-3,6-di-O-sulfo)-beta-cyclodextrin as chiral selectors. For 12 of 16 chiral analytes resolved with both chiral selectors the enantiomer migration order was opposite. In selected cases the structure of cyclodextrin-analyte complexes in aqueous solution was investigated using one-dimensional transverse rotating frame nuclear Overhauser and exchange spectroscopy. It was found that in contrast to mainly inclusion-type complexes between chiral analytes and beta-cyclodextrin, external complexes are formed between the chiral analytes and structurally crowded, highly charged heptakis-(2-O-methyl-3,6-di-O-sulfo)-beta-cyclodextrin.
By the application of a bioassay based on cresson seedlings, two phytotoxic compounds were isolated by thin-layer chromatography from the culture fluid of a Calonectria morganii isolate. The structure of both compounds was elucidated by ESI/MS and NMR spectroscopy. According to the Chemical Abstracts database, they were identified as chaetoglobosin A and 19-O-acetylchaetoglobosin A, mycotoxins originally described for Chaetomium globosum.