4-(1-Haloalkyl)-3-nitrotetrahydrofurans as versatile scaffolds for the synthesis of diversely functionalized tetrahydrofurans

4-(1-Haloalkyl)-3-nitrotetrahydrofurans, which are accessible by tandem oxidative oxa-Michael addition/radical cyclization/ligand transfer reactions, can be processed to diversely substituted tetrahydrofuran derivatives. Selective epimerization at the nitro function provides tetrahydrofuran diastereomers, which cannot be prepared by the tandem process. Intramolecular alkylations furnish interesting bridgehead nitro oxabicyclo[3.1.0]hexane derivatives in high yields. Intermolecular substitution reactions of the halide functions succeed only with nucleophiles, which are not basic enough to trigger intramolecular alkylations. The aryl substituent in 2-aryl-3-nitrotetrahydrofurans can be selectively oxidatively transformed to carboxylic acid derivatives using catalytic Ru(III) and NaIO₄ without affecting the nitro group. Reduction and hydrogenation reactions provide differently substituted 3-aminotetrahydrofuran derivatives depending on the conditions with moderate to good chemoselectivity.     

Oxidative tandem alkoxide conjugate addition to nitroalkenes/radical 5-exo cyclizations—a versatile synthesis of functionalized 3-nitrotetrahydrofurans

Structurally diverse functionalized 4-(1-haloalkyl)-3-nitrotetrahydrofurans were conveniently obtained in moderate to good yield and moderate to very good diastereoselectivity by an oxidative tandem process consisting of conjugate addition reaction of lithium allyloxides to nitroalkenes followed by SET oxidation of the resulting nitronates. This triggers a radical cyclization; ligand transfer from the oxidant provides the products. The influence of the counter ion of the initial alkoxide and intermediate nitronate, the solvent and additives on the outcome of the tandem process was investigated. Optimal conditions for the tandem reactions consist of using butyllithium as the base for deprotonation in DME as the solvent. Cupric halides proved to be the SET oxidants of choice in the tandem reactions. A stereochemical model for the radical cyclization and ligand transfer steps is proposed.     

A Manifold Three‐Step Synthetic Route to Polycyclic Annulated Hydantoins via Cyclic Imines

A new three‐step synthetic pathway to generate polycyclic annulated hydantoins via rarely investigated heterocyclic imines is described. This procedure includes a one‐pot reaction forming imines as precursor structures (e.g., Asinger reaction), followed by an Ugi reaction to build up a bisamide structure that allows a ring‐closing reaction to the targeted hydantoins via substitution. This pathway leads to a multiplicity of substances with a potential pharmacological activity.     

On-line determination of mercury in river water at the German monitoring station Schnackenburg/Elbe

A monitor is described which provides the on-line determination of mercury in river water at concentrations from 20 to 1000 ng/L. The measurement includes an on-line digestion with Br^–/BrO₃ ^– and UV-radiation. Each determination is controlled by an on-line addition of 50 and 100 ng/L mercury carried out by pre-dilution of a 500 and 1000 ng/L stock solution using sequential injection analysis (SIA). One cycle of analysis takes 20 min and results in nine signals. A five days stand-alone operation has been performed successfully. Details are also published at web page: “http/www.rzbd.fh-hamburg.de/¶～prmercol”     

Coordinative Behaviour of Tridentate NS2‐Donor Ligands with Cadmium: Synthesis and Crystal Structures of New Complexes

The reaction of cadmium salts with various amounts of the tridentate NS₂‐chelating ligands 1‐(2‐mercapto‐acetophenone)‐4‐triphenylmethylthiosemicarbazone (H₂L¹) and 1‐(5‐mercapto‐3‐methyl‐1‐phenylpyrazole‐4‐carboxaldehyde)‐4‐triphenyl‐methylthiosemicarbazone (H₂L²) in the presence of bases like N‐methylimidazole (N–MeIm), pyridine (py) or triethylamine (Et₃N) provided a series of novel mono‐, di‐, tri‐ and heptanuclear cadmium complexes. They are of the general formulas [CdL¹(N–MeIm)]₂ ( 1 ), [CdL¹(py)]₂ ( 2 ), [CdL²(N–MeIm)]₂ ( 3 ), [CdL²(py)₃] · 0.25 C₆H₁₄ · 0.5 py ( 4 ), [Et₃NH]₂[Cd₃L ] · 7 MeOH ( 5 ), [Et₃NH]₂[Cd₃L ] ( 6 ) and [Et₃NH]₂[Cd₇L ] · 14 MeOH ( 7 ). The compounds were characterized by elemental analysis, IR‐ and ¹H‐NMR‐spectroscopy. Single‐crystal X‐ray structure analyses are reported for the complexes 2 , 4 , 5 and 7 . While 2 has a dimeric structure where each cadmium ion is pentacoordinated in a N₂S₃‐environment, 4 consists of a monomeric cadmium center with distorted octahedral N₄S₂‐coordination. The complexes 5 and 7 exhibit new structural types for tri‐ and heptanuclear cadmium compounds. It is shown that sulfur bridging might proceed via arylthiolates, iminothiolates or even both functions of the ligand. Aggregation is influenced by various factors like solvents, counterions and ligand properties.     

Patents and literature

Protein engineering and site-directed mutagenesis is becoming immensely important in both fundamental studies and commercial applications involving proteins and enzymes in biocatalysis. Protein engineering has become a powerful tool to help biochemists and molecular enzymologists elucidate structure-function relationships in enzymic active sites, to understand the intricacies of protein folding and denaturation, and to alter the selectivity of enzymatic catalysis. Commercial applications of engineered enzymes are being developed to increase protein stability, widen or narrow substrate specificity, and to develop novel approaches for use of enzymes in organic synthesis, drug design, and clinical applications. In addition to protein engineering, novel expression systems have been designed to prepare large quantities of genetically engineered proteins. Recent US patents and scientific literature on protein engineering, site-directed mutagenesis, and protein expression systems related to protein engineering are surveyed. Patent abstracts are summarized individually and a list of literature references are given.