Palladium-catalysed direct 3- or 4-arylation of thiophene derivatives using aryl bromides

The palladium-catalysed direct 3- or 4-arylation of 2,5-disubstituted thiophenes using aryl bromides gives a simple access to a variety of 3- or 4-arylthiophene derivatives. Moderate to good yields of 3-arylated thiophenes were obtained using 2,5-dimethylthiophene. In the presence of unsymmetrically disubstituted, 2-acetyl-5-methylthiophene, a regioselective arylation on carbon 4 of thiophene was observed. This reaction provides only HX associated to the base as by-product and reduces the number of steps to prepare these compounds.     

Towards the fabrication of label-free amperometric immunosensors using SWNTs

A label-free immunosensor based on the modulation of the electrochemistry of a surface bound redox species, to detect the presence of antibodies, is demonstrated. In this proof of concept study the model epitope was biotin and the model antibody was anti-biotin IgG. Glassy carbon (GC) electrode surfaces were first modified with 4-nitrophenyl groups by electrochemical reductive adsorption of the corresponding aryl diazonium salt. Subsequently, the nitro group was reductively converted into an amine, giving 4-aminophenyl groups. Oxidatively shortened single walled carbon nanotubes (SWNTs) were then covalently attached to the electrode via self-assembly; a procedure that has previously been shown to give SWNTs aligned normal to the surface. 1,1-Di(aminomethyl)ferrocene was attached to the carboxylic acid terminated SWNTs followed by attachment of biotin to the remaining free amine of the ferrocene derivative. Binding of anti-biotin IgG to the surface bound epitope resulted in attenuation of the ferrocene electrochemistry. This label-free immunosensor was successfully able to detect anti-biotin between 30 and 450 ng mL⁻¹.     

Assessing indoor air exposures using passive sampling with bioanalytical methods for estrogenicity and aryl hydrocarbon receptor activity

Passive air sampling was undertaken using polyurethane foam passive air samplers at three types of locations, including indoors (six offices) at buildings in the central business district (CBD) and at a private suburban home (indoor and outdoor) located 9 km from the CBD in Brisbane, Queensland, Australia. Estrogenic (E-SCREEN—MCF7-BOS) and aryl hydrocarbon receptor (AhR) (CAFLUX—H4G1.1c2) activity were assessed for samples collected from each of these locations. The samples were tested either as crude extracts (“untreated”) or were subjected to H₂SO₄ silica gel (“treated”) for each location in order to determine whether chemicals, which are not resistant to this treatment like polycyclic aromatic hydrocarbons, potentially account for the observed activity. In most cases, H₂SO₄ treatment resulted in a statistically significant reduction of potency for both endpoints, suggesting that chemicals less resistant to treatment may be responsible for much of the detected biological activity in these locations. Estrogenic potency measurements (<0.22–185 pg m⁻³) were highest in the indoor offices, followed by the indoor suburban home and finally the outdoor suburban home (which was not estrogenic). Total AhR activity for crude extracts (1.3–10 pg m⁻³) however was highest for the outdoor suburban home site. Levels of polycyclic aromatic hydrocarbons were monitored indoors and outdoors at the suburban home. At that location, polycyclic aromatic hydrocarbon air concentrations were on average approximately two times higher outdoor than indoor, while AhR potency was five times higher outdoor than indoor. No significant correlation was found between the estrogenic and AhR activity (P = 0.88) for the sites in this study. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Microwave‐Assisted Cross‐Coupling for the Construction of Diaryl Sulfides

The construction of diaryl sulfides through the cross‐coupling of aryl iodides and thiols in microwave heating is described. By using this method, a variety of diaryl sulfides can be prepared in a mild condition and in high yields. Deactivated 4‐nitrothiophenol was effective to afford the product in 94% yield. Sterically hindered ortho‐substituted aryl iodides or thiophenols provided diaryl sulfides effectively by this microwave‐assisted coupling reaction.     

Reactions of [η-carboxycyclopentadiene][η-tetraphenylcyclo butadiene] cobalt with alkyl and aryl tin oxides: Synthesis, structural studies and electrochemistry of novel monomeric and dimeric [η-carboxycyclopentadiene][η-tetraphenylcyclobutadiene]cobalt based stannoxanes

Reactions of [η⁵-carboxycyclopentadienyl][η⁴-tetraphenylcyclobutadiene] cobalt, Ph₄C₄CoC₅H₄COOH (1), with (Ph₃Sn)₂O, [(n-Bu)₂SnO]_n and (Ph₂SnO)_n in refluxing toluene resulted in the formation of the monomeric compound Ph₃SnOC(O)C₅H₄CoC₄Ph₄ (2) and dimeric compounds n-Bu₂Sn[OC(O)C₅H₄CoC₄Ph₄]₂ (3) and Ph₂Sn[OC(O)C₅H₄CoC₄Ph₄]₂ (4), respectively. Reactions carried out in the solid state by mechanical grinding also yielded same results. Crystal structure determination and cyclic voltammetric studies of compounds 1, 2, 3 and 4 have been carried out and compared with similar ferrocene carboxylic acid derivatives. The structures and electrochemistry of these compounds are compared with analogous organotin ferrocene carboxylates. The results obtained from the reaction of 1 with alkyl and aryl tin oxides suggest that the formation of stannoxanes assemblies having more than two carboxylate units are not favored indicating that 1 is a highly sterically hindered metallocene carboxylic acid.     

Synthesis and characterization of bis[dicarboxylatotetraorganodistannoxane] units involving 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids: An investigation of structures by X-ray diffraction, NMR, electrospray ionisation MS and assessment of in vitro cytotoxicity

Reactions of 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids (LHH′, where the aryl group is an R-substituted phenyl ring such that for L¹HH′: R = H; L²HH′: R = 2′-CH₃; L³HH′: R = 3′-CH₃; L⁴HH′: R = 4′-CH₃; L⁵HH′: R = 4′-Cl; L⁶HH′: R = 4′-Br) with ⁿBu₂SnO in a 1:1 molar ratio yielded complexes of composition {[ⁿBu₂Sn(LH)]₂O}₂. The complexes have been characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, ESI-MS, IR and ^119mSn Mössbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of {[ⁿBu₂Sn(L¹H)]₂O}₂ (1), {[ⁿBu₂Sn(L⁴H)]₂O}₂ (4), {[ⁿBu₂Sn(L⁵H)]₂O}₂ (5) and {[ⁿBu₂Sn(L⁶H)]₂O}₂ (6) were determined. The compounds are centrosymmetric tetranuclear bis(dicarboxylatotetrabutyldistannoxane) complexes containing a planar Sn₄O₂ core in which two μ₃-oxo O-atoms connect an Sn₂O₂ ring to two exocyclic Sn-atoms. The four carboxylate ligands display two different modes of coordination where both modes involve bridging of two structurally distinct Sn-atoms. The solution structures were confirmed by ¹¹⁹Sn NMR spectroscopy by observing two tin resonances in compounds 1, and 4-6. The observed difference between the two tin resonances was about 3 ppm while the differences in ¹³C resonances were even smaller. Compounds {[ⁿBu₂Sn(L²H)]₂O}₂ (2) and {[ⁿBu₂Sn(L³H)]₂O}₂ (3) undergo a very complex exchange processes in deuteriochloroform solution. The in vitro cytotoxic activity of compounds 1 and 4 against WIDR, M19 MEL, A498, IGROV, H226, MCF7 and EVSA-T human tumour cell lines is reported.     

CuI‐Mediated Trifluoromethylations with Stannanes. Preliminary Communication

(Trifluoromethyl)stannane reagents such as Bu₃SnCF₃ are effective in CuI‐mediated trifluoromethylation reactions of aryl iodides. The reactions proceed via the intermediacy of [CuCF₃] species.     

An expedient route for the reduction of carboxylic acids to alcohols employing 1-propanephosphonic acid cyclic anhydride as acid activator

A simple and efficient method for the synthesis of alcohols from the corresponding carboxylic acids is described. Activation of carboxylic acid with 1-propanephosphonic acid cyclic anhydride (T3P) and subsequent reduction using NaBH₄ yield the alcohol in excellent yields with good purity. Reduction of several alkyl/aryl carboxylic acids and N^α-protected amino acids/peptide acids as well as N^β-protected amino acids was successfully carried out to obtain corresponding alcohols in good yields. All the products were fully characterized by ¹H NMR and mass spectral analyses. The procedure is mild, simple and the isolation of the products is easy.     

N-Bromosuccinimide as an efficient catalyst for the synthesis of indolo[2,3-b]quinolines

The use of N-bromosuccinimide as a catalyst promoted the synthesis of polycyclic indolo[2,3-b]quinoline derivatives in good to high yields in the reactions of various aryl amines with indole-3-carbaldehyde at room temperature under mild conditions.     

NaIO4-NaN3-mediated diazidation of styrenes, alkenes, benzylic alcohols, and aryl ketones

Sodium periodate and sodium azide combination has been found to be an excellent reagent system suitable for the direct diazidation of styrenes, alkenes, benzylic alcohols, and aryl ketones to produce the corresponding vicinal and geminal diazides respectively in high yields under mild reaction conditions.