Synthesis,structure and catalytic properties of bis[2‐(trifluoromethyl)phenyl]silanediol

A novel trifluoromethylaryl‐substituted disilanol, bis[(2‐trifluoromethyl)phenyl] silanediol, was prepared by hydrolysis of the precursor dichloride and fully characterized. Single‐crystal X‐ray diffraction indicates doubly linked hydrogen bonded dimers and also hydrogen bonding to tetrahydrofuran solvent. The acidity of the silanol functions is enhanced by the presence of the trifluoromethyl groups and the compound is found to be active in promoting a standard Diels–Alder reaction, increasing yields by a factor of three.     

New ring-linear codes from dualization in projective Hjelmslev geometries

In this article, several new constructions for ring-linear codes are given. The class of base rings are the Galois rings of characteristic 4, which include ${\mathbb {Z}_4}$ as its smallest and most important member. Associated with these rings are the Hjelmslev geometries, and the central tool for the construction is geometric dualization. Applying it to the ${\mathbb {Z}_4}$ -preimages of the Kerdock codes and a related family of codes we will call Teichmüller codes, we get two new infinite series of codes and compute their symmetrized weight enumerators. In some cases, residuals of the original code give further interesting codes. The generalized Gray map translates our codes into ordinary, generally non-linear codes in the Hamming space. The obtained parameters include (58, 2⁷, 28)₂, (60, 2⁸, 28)₂, (114, 2⁸, 56)₂, (372, 2¹⁰, 184)₂ and (1988, 2¹², 992)₂ which provably have higher minimum distance than any linear code of equal length and cardinality over an alphabet of the same size (better-than-linear, BTL), as well as (180, 2⁹, 88)₂, (244, 2⁹, 120)₂, (484, 2¹⁰, 240)₂ and (504, 4⁶, 376)₄ where no comparable (in the above sense) linear code is known (better-than-known-linear, BTKL).     

tert‐Amino effect at a coumarin and a 2‐quinolone system: Synthesis of 1,2 fused 5H‐chromeno[4,3‐b]pyridin‐5‐ones and a 6H‐benzo[h][1,6]naphthyridin‐5‐one

Some novel 1,2‐fused 5H‐chromeno[4,3‐b]pyridin‐5‐ones ( 5a,b ) and a 6H‐benzo[h][1,6]naphthyridin‐5‐one ( 5c ) have been synthesized starting from the 4‐chlorocoumarin‐3‐carbaldehyde ( 1a ) or its N‐methyl‐2‐quinolone analogue ( 1b ) via subsequent Knoevenagel condensation and ring closure reaction known as the ‘tert‐amino effect’. These are rare examples of the tert‐amino effect occurring at 2‐pyrone and 2‐pyridone ring. An unusual intramolecular redox reaction of the iminium ion 6 , reported earlier, most probably follows analogous mechanism as the tert‐amino effect reactions leading to 5 .     

Biosynthesis of isoprenoids. purification and properties of IspG protein from Escherichia coli

[Structure: see text]. The IspG protein is known to catalyze the transformation of 2-C-methyl-d-erythritol 2,4-cyclodiphosphate into 1-hydroxy-2-methyl-2-(E)-butenyl 4-diphosphate in the nonmevalonate pathway of isoprenoid biosynthesis. We have found that the apparent IspG activity in the cell extracts of recombinant Escherichia coli cells as observed by a radiochemical assay can be enhanced severalfold by coexpression of the isc operon which is involved in the assembly of iron-sulfur clusters. The recombinant protein was isolated by affinity chromatography under anaerobic conditions. With a mixture of flavodoxin, flavodoxin reductase, and NADPH as the reducing agent, stringent assay methods based on photometry or on 13C NMR detection of multiply 13C-labeled substrate/product ratios afforded catalytic activities greater than 60 nmol mg(-1) min(-1) for the protein "as isolated" (i.e., without reconstitution of any kind). Lower apparent activities were found using photoreduced deazaflavin as an artifactual electron donor, whereas dithionite was unable to serve as an artificial electron donor. The apparent Michaelis constant for 2-C-methyl-D-erythritol 2,4-cyclodiphosphate was 700 microM. The enzyme was inactivated by EDTA and could be reactivated by Mn2+. The pH optimum was at 9.0. The protein contained 2.4 iron ions and 4.4 sulfide ions per subunit. The replacement of any of the three conserved cysteine residues afforded mutant proteins which were devoid of catalytic activity and contained less than 6% of Fe2+ and less than 23% of S2- as compared to the wild-type protein. Sequence comparison indicates that putative IspG proteins of plants, the apicomplexan protozoan Plasmodium falciparum, and bacteria from the Bacteroidetes/Chlorobi group contain an insert of about 170-320 amino acid residues as compared with eubacterial enzymes.     

Pyridazine based scorpionate ligand in a copper boratrane compound

Reaction of potassium tris(mercapto-tert-butylpyridazinyl)borate K[Tn(tBu)] with copper(II) chloride in dichloromethane at room temperature led to the diamagnetic copper boratrane compound [Cu{B(Pn(tBu))(3)}Cl] (Pn = pyridazine-3-thionyl) (1) under activation of the B-H bond and formation of a Cu-B dative bond. In contrast to this, stirring of the same ligand with copper(I) chloride in tetrahydrofuran (THF) gave the dimeric compound [Cu{Tn(tBu)}](2) (2) where one copper atom is coordinated by two sulfur atoms and one hydrogen atom of one ligand and one sulfur of the other ligand. Hereby, no activation of the B-H bond occurred but a 3-center-2-electron B-H···Cu bond is formed. The reaction of copper(II) chloride with K[Tn(tBu)] in water gave the same product 2, but a formal reduction of the metal center from Cu(II) to Cu(I) occurred. When adding tricyclohexyl phosphine to the reaction mixture of K[Tn(R)] (R = tBu, Me) and copper(I) chloride in MeOH, the distorted tetrahedral Cu complexes [Cu{Tn(R)}(PCy(3))] (R = tBu 3, Me 4) were formed. Compound 4 is exhibiting an "inverted" κ(3)-H,S,S, coordination mode. The copper boratrane 1 was further investigated by density functional theory (DFT) calculations for a better understanding of the M→B interaction involving the d(8) electron configuration of Cu.     

Activation and Photoinduced Release of Alkynes on a Biomimetic Tungsten Center: The Photochemical Behavior of the W−S-Phoz System

The synthesis and structural determination of four tungsten alkyne complexes coordinated by the bio-inspired S,N-donor ligand 2-(4′,4′-dimethyloxazoline-2′-yl)thiophenolate (S-Phoz) is presented. A previously established protocol that involved the reaction of the respective alkyne with the bis-carbonyl precursor [W(CO)₂(S-Phoz)₂] was used for the complexes [W(CO)(C₂R₂)(S-Phoz)₂] (R=H, 1 a ; Me, 1 b ; Ph, 1 c ). Oxidation with pyridine-N-oxide gave the corresponding W-oxo species [WO(C₂R₂)(S-Phoz)₂] (R=H, 2 a ; Me, 2 b ; Ph, 2 c ). All W-oxo-alkyne complexes ( 2 a , b , c ) were found to be capable of alkyne release upon light irradiation to afford five-coordinate [WO(S-Phoz)₂] ( 3 ). The photoinduced release of the alkyne ligand was studied in detail by in situ ¹H NMR measurements, which revealed correlation of the photodissociation rate constant ( 2 b>2 a>2 c ) with the elongation of the alkyne C≡C bond in the molecular structures. Oxidation of [WO(S-Phoz)₂] ( 3 ) with pyridine-N-oxide yielded [WO₂(S-Phoz)₂] ( 4 ), which shows highly fluxional behavior in solution. Variable-temperature ¹H NMR spectroscopy revealed three isomeric forms with respect to the ligand arrangement versus each other. Furthermore, compound 4 rearranges to tetranuclear oxo compound [W₄O₄(μ-O)₆(S-Phoz)₄] ( 5 ) and dinuclear [{WO(μ-O)(S-Phoz)}₂] ( 6 ) over time. The latter two were identified by single-crystal X-ray diffraction analyses.     

Elektronenstossinduzierte Fragmentierung von Acetylenverbindungen—IV: Mechanistische Betrachtungen zur Bildung des Benztropyliumkations aus den Chlormethyl-Naphthalinen und 1-Chlor-Phenyl-(5)-Penten-(2)-in-(4)

Mass spectroscopic investigations of ²H- and ¹³C-labelled derivatives of e.g. 1-, 2-chloro-methyl-naphthalene and 1-chloro-phenyl(5)-pentene-(2)-in-(4) show that the [C₁₁H₉]⁺ ion, which gives [C₉H₇]⁺ by acetylene elimination, has the structure of a benztropylium cation. Model considerations show that the formation of this cation [C₁₁H₉]⁺ through a common transition state with a three-membered ring is very probable.