- Nucleoside analogues with a 1,3-diene-Fe(CO)3 substructure: Stereoselective synthesis, configurational assignment, and apoptosis-inducing activity
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The synthesis and stereochemical assignment of two classes of iron-containing nucleoside analogues, both of which contain a butadiene-Fe(CO)3 substructure, is described. The first type of compounds are Fe(CO)3-complexed 3'-alkenyl-2′,3′-dideoxy- 2′,3′-dehydro nucleosides (2,5-dihydrofuran derivatives), from which the second class of compounds is derived by formal replacement of the ring oxygen atom by a CH2 group (carbocyclic nucleoside analogues). These compounds were prepared in a stereoselective manner through the metal-assisted introduction of the nucleobase. Whilst the furanoid intermediates were prepared from carbohydrates (such as methyl-glucopyranoside), the carbocyclic compounds were obtained by using an intramolecular Pauson-Khand reaction. Stereochemical assignments based on NMR and CD spectroscopy were confirmed by X-ray structural analysis. Biological investigations revealed that several of the complexes exhibited pronounced apoptosis-inducing properties (through an unusual caspase 3-independent but ROS-dependent pathway). Furthermore, some structure-activity relationships were identified, also as a precondition for the design and synthesis of fluorescent and biotin-labeled conjugates. I gotta Fe-ling: Iron-containing nucleoside analogues, which were first synthesized during an exercise in stereoselective π-complex chemistry, exhibited pronounced cytotoxic and apoptosis-inducing activities, even against resistant cancer cell lines. Both hetero- (X=O) and carbocyclic (X=CH2) compounds were studied, and a synthetic route to R′-labeled derivatives was developed as a precondition for future biological experiments. TDS=thexyldimethylsilyl. Copyright
- Hirschh?user, Christoph,Velcicky, Juraj,Schlawe, Daniel,Hessler, Erik,Majdalani, André,Neud?rfl, J?rg-Martin,Prokop, Aram,Wieder, Thomas,Schmalz, Hans-Günther
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supporting information
p. 13017 - 13029
(2013/10/01)
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- Regio- and Stereoselective Ring Opening of Epoxy Pyranosides with Titanium Isopropoxide Reagents and SmI2: A Straightforward Access to Iododeoxy Sugars
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A regioselective synthesis of 3-iodo-3-deoxy sugars is described by trans-diaxial cleavage of the oxirane ring of 2,3-anhydropyranosides with halogenated titanium isopropoxide reagents and samarium iodide.
- Khan, Noshena,Al-Abed, Yousef,Kohlbau, Hans-Juergen,Latif-Ansari, Farzana,Kowollik, Wolfgang,Voelter, Wolfgang
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p. 1781 - 1790
(2007/10/03)
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- Solid Phase Synthesis of Muramyl Dipeptide Derivatives and Investigations on their Biological Activities
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New muramyl dipeptide derivatives with exchanged carbohydrate residues are described.Each derivative is synthesized via a solid phase synthesis using an aminomethyl anchor resin.All synthetic products can be isolated in good yields.Their biological activities are tested by the luminol-dependent chemiluminescence associated with the phagocytosis of opsonized zymosan by granulocytes. - Keywords: Muramyl Dipeptide, Solid Phase Synthesis, Chemiluminescence, Glycopeptide Derivatives
- Tschakert, Jochen,Voelter, Wolfgang
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p. 702 - 716
(2007/10/02)
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- An Approach to Chiral η4-Butadiene-Fe(CO)3 Complexes via Diastereoselective Complexation of Nonracemic 2-Alkoxy-4-vinyl-2,5-dihydrofuran Derivatives
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Complexation of (+)-L-arabinose-derived 2-benzyloxy-4-vinyl-2,5-dihydrofuran derivatives (8) with Fe2(CO)9 in ether proceeds diastereoselectively providing a (separable) mixture of the corresponding exo- and endo- η4-diene-Fe(CO)3 complexes 9 and 10 in a ratio of about 1 : 3.The relative (and absolute) configuration of the complexation products was determined by a combination of analytical methods (CD, NMR, X-ray).
- Schmalz, Hans-Guenther,Hessler, Erik,Bats, Jan W.,Duerner, Gerd
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p. 4543 - 4546
(2007/10/02)
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- Efficient High-Yielding Syntheses and NMR Spectroscopic Studies of Some Fluorodeoxy Sugars
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Displacement of the triflyl group by fluoride ion in benzyl 2,3-anhydro-4-O-(trifluoromethylsulfonyl)pyranosides 1-3 leads with stereochemical inversion to the 4-fluoro-4-deoxy sugars 4-6, providing a general method for the introduction of fluorine in the
- Latif, Farzana,Malik, Abdul,Voelter, Wolfgang
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p. 617 - 620
(2007/10/02)
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