The first one-pot ‘alkane-like’ reactions of carbonyl-containing adamantanes

A novel ‘alkane-like’ methodology for the direct and very simple one-pot functionalization of amides and an ester of 1-adamantanecarboxylic acid provides access to new and synthetically challenging 1,3-dicarbonyl-containing adamantanoid compounds with the same or different functional groups.     

Niementowski-type synthesis of pyrido[3,2-e][1,2,4]triazines: potent aza-analogs of pyrido[2,3-b]pyrazine fungicides

Novel trisubstituted pyrido[3,2-e][1,2,4]triazines have been found to possess similar biological activity to the corresponding pyridopyrazine fungicides against important phytopathogens such as Mycosphaerella graminicola (wheat leaf blotch), Magnaporthe grisea (rice blast), and Rhizoctonia solani (rice sheath blight). They have been prepared for the first time from a monocyclic triazine by Niementowski-type ring condensation.     

Stereoselective 6π-electron electrocyclic ring closures of 2-halo-amidotrienes via a remote 1,6-asymmetric induction

A diastereoselective 6π-electrocyclic ring closure employing halogen-substituted 3-amidotrienes via a 1,6-remote asymmetric induction is described. This new asymmetric manifold for pericyclic ring closure further underscores the significance of the allenamide chemistry.     

Dual functional polyelectrolyte multilayer coatings for implants: permanent microbicidal base with controlled release of therapeutic agents

Here we present a new bifunctional layer-by-layer (LbL) construct made by combining a permanent microbicidal polyelectrolyte multilayered (PEM) base film with a hydrolytically degradable PEM top film that offers controlled and localized delivery of therapeutics. Two degradable film architectures are presented: (1) bolus release of an antibiotic (gentamicin) to eradicate initial infection at the implant site, or (2) sustained delivery of an anti-inflammatory drug (diclofenac) to cope with inflammation at the site of implantation due to tissue injury. Each degradable film was built on top of a permanent base film that imparts the implantable device surface with microbicidal functionality that prevents the formation of biofilms. Controlled-delivery of gentamicin was demonstrated over hours and that of diclofenac over days. Both drugs retained their efficacy upon release. The permanent microbicidal base film was biocompatible with A549 epithelial cancer cells and MC3T3-E1 osteoprogenitor cells, while also preventing bacteria attachment from turbid media for the entire duration of the two weeks studied. The microbicidal base film retains its functionality after the biodegradable films have completely degraded. The versatility of these PEM films and their ability to prevent biofilm formation make them attractive as coatings for implantable devices.     

Asymmetric synthesis of fluorine-containing amines, amino alcohols, α- and β-amino acids mediated by chiral sulfinyl group

This review article provides a critical overview of several different synthetic approaches developed for asymmetric preparation of fluorine-containing amines, amino alcohols, α- and β-amino acids. The common feature of these methods is the application of sulfinyl group as a chiral auxiliary to control the stereochemical outcome of the reactions under study. In particular, the following general methods are critically discussed: diastereoselective methylene transfer from diazomethane to the carbonyl of β-keto-γ-fluoroalkyl sulfoxides as a general approach for preparation of various α-fluoroalkyl α-sulfinylalkyl oxiranes. The resulting compounds were used as true chiral synthons for their further elaboration via oxidative or reductive desulfurization, to numerous fluorine-containing and biologically relevant amino- and hydroxy-containing derivatives. Another general approaches discussed here are asymmetric additions to CN double bond. One of them is addition of chiral sulfoxide stabilized carbon nucleophiles to fluorine-containing imines, leading to convenient preparation of alpha-fluoroalkyl derivatives of alpha amino acids and amines. Another approach is asymmetric Reformatsky reaction between N-sulfinyl imines and ethyl bromodifluoroacetate allowing operationally convenient preparation of α,α-difluoro-β-amino acids in enantiomerically pure form. Finally, structurally similar but mechanistically different addition reactions of diethyl difluoromethylphosphonate to N-sulfinyl imines, as a general approach to asymmetric synthesis of α,α-difluoro-β-aminophosphonates and phosphonic acids, are discussed. Effect of fluorine on the mechanism and stereochemical outcome of these reactions is discussed in detail and compared, where it is possible, with that of the analogous reactions of fluorine-free substrates.     

(Mesitylene)ruthenium π-complexes with benzo-15-crown-5 and dibenzo-18-crown-6

The reactions of benzo-15-crown-5 and dibenzo-18-crown-6 with 1 equiv. of [(mes)Ru(MeNO₂)₃]²⁺ (mes = 1,3,5-C₆H₃Me₃) give the mononuclear complexes [(mes)Ru(η⁶-benzo-15-crown-5)]²⁺ (1) and [(mes)Ru(η⁶-dibenzo-18-crown-6)]²⁺ (2) in 50% yield. Similar reaction with 2 equiv. of [(mes)Ru(MeNO₂)₃]²⁺ produces the dinuclear complex [(μ-η⁶:η⁶-dibenzo-18-crown-6)Ru₂(mes)₂]⁴⁺ (3) in 96% yield as a 2:3 mixture of cis- and trans-isomers. Structures of 2(OTf)₂ and trans-3(OTf)₄ were confirmed by X-ray diffraction. The NMR titration showed that mononuclear dications 1 and 2 bind Na⁺ ion less effective (K_a = 600 and 250 M^-1) than free benzo-15-crown-5 and dibenzo-18-crown-6 (K_a = 2 × 10⁵ and 5 × 10⁶ M⁻¹). The dinuclear tetracation 3 does not bind Na⁺ within measurable limits of NMR titration method. The electrochemical behaviour of complexes 1-3 was studied in propylene carbonate solution. They exhibit a partially chemically reversible Ru(II)/Ru(I) reduction, which in the case of the dinuclear complex 3 proceeds through two slightly separated steps. The redox activity of the complexes is substantially unaffected by the presence of sodium ion.     

Ethynylmonocarba-closo-dodecaborates: M[12-HCC-closo-1-CB11H11] and M[7,12-(HCC)2-closo-1-CB11H10] (M = Cs, [Et4N])

Cesium and tetraethylammonium salts of the ethynyl functionalized monocarba-closo-dodecaborate anions [12-HCC-closo-1-CB₁₁H₁₁]⁻ and [7,12-(HCC)₂-closo-1-CB₁₁H₁₀]⁻ were obtained by desilylation of [Et₄N][12-Me₃SiCC-closo-1-CB₁₁H₁₁] and [Et₄N][7,12-(Me₃SiCC)₂-closo-1-CB₁₁H₁₀], respectively. Their thermal properties were examined by differential scanning calorimetry. The compounds were characterized by multi-NMR, IR, and Raman spectroscopy, (−)-MALDI mass spectrometry, and elemental analysis. Single-crystals of Cs[12-HCC-closo-1-CB₁₁H₁₁] and [Et₄N][7,12-(HCC)₂-closo-1-CB₁₁H₁₀] were studied by X-ray diffraction. The discussion of the spectroscopic and structural properties is supported by data derived from theoretical calculations using density functional theory as well as perturbation theory.     

The ternary system cerium-rhodium-silicon

Phase relations have been established in the ternary system Ce-Rh-Si for the isothermal section at 800 °C based on X-ray powder diffraction and EPMA on about 80 alloys, which were prepared by arc melting under argon or by powder reaction sintering. From the 25 ternary compounds observed at 800 °C 13 phases have been reported earlier. Based on XPD Rietveld refinements the crystal structures for 9 new ternary phases were assigned to known structure types. Structural chemistry of these compounds follows the characteristics already outlined for their prototype structures: τ₇—Ce₃RhSi₃, (Ba₃Al₂Ge₂-type), τ₈—Ce₂Rh_3−xSi_3+x (Ce₂Rh_1.35Ge_4.65-type), τ₁₀—Ce₃Rh_4−xSi_4+x (U₃Ni₄Si₄-type), τ₁₁—CeRh₆Si₄ (LiCo₆P₄-type), τ₁₃—Ce₆Rh₃₀Si_19.3 (U₆Co₃₀Si₁₉-type), τ₁₈—Ce₄Rh₄Si₃ (Sm₄Pd₄Si₃-type), τ₂₁—CeRh₂Si (CeIr₂Si-type), τ₂₂—Ce₂Rh_3+xSi_1−x (Y₂Rh₃Ge-type) and τ₂₄—Ce₈(Rh_1−xSi_x)₂₄Si (Ce₈Pd₂₄Sb-type). For τ₂₅—Ce₄(Rh_1−xSi_x)₁₂Si a novel bcc structure was proposed from Rietveld analysis. Detailed crystal structure data were derived for τ₃—CeRhSi₂ (CeNiSi₂-type) and τ₆—Ce₂Rh₃Si₅ (U₂Co₃Si₅-type) by X-ray single crystal experiments, confirming the structure types. The crystal structures of τ₄—Ce₂₂Rh₂₂Si₅₆, τ₅—Ce₂₀Rh₂₇Si₅₃ and τ₂₃—Ce_33.3Rh_58.2−55.2Si_8.5−11.5 are unknown. High temperature compounds with compositions Ce₁₀Rh₅₁Si₃₃ (U₁₀Co₅₁Si₃₃-type) and CeRhSi (LaIrSi-type) have been observed in as-cast alloys but these phases do not participate in the phase equilibria at 800 °C.     

Raman Spectra of Tungsten-Bearing Solutions

Raman spectroscopy at 25 °C was performed to analyze speciation in quenched solutions after experiments on sodium tungstates and sodium tungstate bronze dissolution at t=500 °C, p=1000 bar. The experiments were conducted under different oxidation-reduction conditions in sodium chloride solution media. The spectra of the quenched solutions were different from those of the reference solutions of 0.02 mol⋅kg⁻¹ W(VI) (H₂O) in the pH range 2.3–7.2. Thermodynamic models were established and the fields of predominance of different isopolytungstate species at 25–50 °C were determined. The experimental results of tungstate dissolution demonstrates that reduced tungstate solutions may contain a significant amount of tungsten species with valence states lower than W(VI).     

Preparation of pure hydrogen peroxide and anhydrous peroxide solutions from crystalline serine perhydrate

Hydrogen peroxide is one of the most versatile oxidation reagents, still it has not fully been exploited by synthetic chemists since anhydrous (let alone pure) hydrogen peroxide requires hazardous preparation protocols. We have recently reported on the crystallization of serine and other amino acid perhydrates, thus paving the way for a new method for laboratory-scale production of anhydrous hydrogen peroxide solutions. Serine is insoluble in most organic solvents (e.g., methanol, ethyl acetate, and methyl acetate) that readily dissolve hydrogen peroxide. Moreover, since the adduct of hydrogen peroxide and serine is unstable in these organic solvents, crystalline serine perhydrate readily decomposes to give anhydrous solutions of hydrogen peroxide and crystalline precipitate of the amino acid. This procedure can then yield an anhydrous hydrogen peroxide solution in a single step. Moreover, filtration of the amino acid, and room temperature evaporation of the volatile solvent (e.g., methyl acetate), yields over 99% hydrogen peroxide.