The quest for single-enantiomer outcomes in free-radical chemistry

A significant challenge facing free-radical chemists is in the area of stereocontrol, specifically the ability to control the direction of reagent attack at a prochiral radical. While significant inroads have been made in the area of diastereoselective radical chemistry, less successful have been attempts to provide truly enantioselective processes. This article highlights recent efforts in the area of enantioselective free-radical reduction chemistry and describes how single-enantiomer outcomes are possible when simple enantiopure stannanes are used in conjunction with large, sterically-demanding Lewis acids. Selectivities in excess of 90% are now possible, with one example in excess of 99.5% ee provided.

Single enatiomer free-radical chemistry - Lewis acid-mediated reductions of racemic halides using chiral non-racemic stannanes

Additions of one to two equivalents of Lewis acids that include magnesium salts to free-radical reduction reactions involving ester functionalized radicals and (1R,2S,5R)-menthyldiphenyltin hydride 4, bis((1R,2S,5R)-menthyl)phenyltin hydride 5, tris((1R,2S,5R)-menthyl)tin hydride 6, bis((1R,2S,5R)-menthyl)-[8-(N,N-dimethylamino)naphthyl]tin hydride 12, bis((1R,2S,5R)-menthyl)-[1-((S)-N,N-dimethylaminoethyl)phenyl]tin hydride 13 or 3α-dimethylstannyl-5α-cholestane 14 result in remarkable enantioselectivities. Examples include (S)-naproxen ethyl ester 16, produced in 74% yield and greater than 99% ee at −78°C from the bromide and 5 in the presence of MgBr₂, and ethyl (R)-N-trifluoroacetyl-_D-phenylglycinate 18, obtained in 78% yield and 99% ee under identical conditions. Kinetic and computational studies provide insight into the origins of these observations.

Media/ting change: the print media's role in mediating education policy in a period of radical reform in Victoria, Australia

This paper draws upon critical discourse analysis, cultural studies and communication theory, studies on media and educational reform, and the work of Bernstein, Bourdieu and Luhmann in particular, to explore how the print and media 'mediated' a period of educational change marked by moves to self-management in schools in Victoria, Australia. It considers how the media was mobilized by various education stakeholders, and in turn informed relations between schools and government, through policy discourses and texts. It considers why and how particular themes became media 'issues', how schools and teachers responded to these issues, and how the media was used by various stakeholders in education to shape policy debates. It is based on a year-long qualitative study that explored critical incidents and representations about education in the print media over a year in the daily press. It illustrates the ways in which a neo-liberal Victorian government mobilized the media to gain strategic advantage to promote radical education reform policies, considers the media effects of this media/tion process on schools and teachers, and conceptualizes how school and system performance is fed from and into media representations, public perceptions and community understandings of schools and teachers' work.

Synthesis, polymerization and wool coating studies of 3-iso-butylpyrrole and 3-iso-pentylpyrrole

In a four-step method starting from pyrrole, the synthesis of 3-iso-butylpyrrole and 3-iso-pentylpyrrole, was achieved in 45 and 44% yields, respectively. Polymerization studies of these branched alkyl pyrroles are described and the results compared with those obtained for the unbranched structural isomers n-butyl and n-pentylpyrrole. A series of conductive textiles were produced by the chemical polymerization of the iso-alkylpyrroles using both solution and vapour polymerization techniques. Fabrics coated with poly-iso-alkylpyrrole formed using the solution polymerization method had a lower surface resistance than those formed using the vapour polymerization method. These conductivity results were in direct contrast to those previously obtained for 3-n-alkylpyrroles on fabrics. A remarkable crystal-like growth on the surface of the textile fabric was observed when solution polymerization of 3-iso-pentylpyrrole was employed—reinforcing the notion that subtle changes in monomer structure can drastically affect bulk polymer properties.

Conductive wool yarns by continuous vapour phase polymerization of pyrrole

Conducting polypyrrole (PPy) coated wool yarns were prepared by a continuous vapour polymerization technique, using a speed of 1 m/min with different iron(III) chloride (FeCl₃) as the oxidant at different concentrations. The resistivities, tensile properties, longitudinal and cross-sectional views of PPy-coated wool yarns were investigated. Optimum specific electrical resistances of 2.96 Ω g/cm² at 80 g/L FeCl₃ and 1.69 Ω g/cm² at 70 g/L FeCl₃ were obtained for 500 and 400 twist per meter (TPM) yarns, respectively. PPy-coated wool yarns exhibited higher elongation than uncoated yarns. Longitudinal and cross-sectional views of the yarns indicate that PPy coating penetrated deep into the yarn cross-section and a uniform coating was obtained on the surface of the yarn surface.

Synthesis and polymerization studies of 3-(+) and (-) -menthyl carboxylate pyrroles

The synthesis of 3-(−)- and 3-(+)-menthyl carboxylate pyrrole was achieved in four high yielding steps, including the triisopropylsilyl (TIPS) protection of the pyrrole nitrogen, bromination of the 3-position, lithium halogen exchange followed by reaction with menthyl chloroformate, and finally de-protection. Chemical polymerization of both the TIPS protected, and non-protected, menthyl carboxylate pyrroles was performed and the resulting polymers exhibited conductivity ranging from 0.6 to 2.3 S/cm. Polymerization of the 3-menthyl-N-TIPS pyrrole on the surface of wool was achieved by using solution and mist polymerization methods.

Synthesis, characterization and enantioselective free radical reductions of (1R,2S,5R)-menthyldiphenylgermane and its enantiomer

(1R,2S,5R)-Menthyldiphenylgermane and its enantiomer have been prepared in a few steps from germanium tetrachloride. The initial step in this sequence, namely the reaction between germanium tetrachloride and menthylmagnesium chloride, produces menthylgermanium trichloride, which is the exclusive product of this Grignard reaction, presumably due to the bulk of the menthyl group. When used at a low temperature (−78 °C) and in conjunction with Lewis acids, such as magnesium salts, these chiral germanes are capable of reducing ester functionalized radicals in high enantioselectivity, but in low-moderate yield. For example, (R)-naproxen ethyl ester was obtained in 15% yield and 99% ee by reaction in toluene of 2-bromonaproxen ethyl ester with (1R,2S,5R)-menthyldiphenylgermane in toluene at −78 °C in the presence of magnesium bromide. At 80 °C, (1R,2S,5R)-menthyldiphenylgermane reacted with primary alkyl radicals with a rate constant of 1.02 × 10⁶ M⁻¹ s⁻¹. Kinetic studies reveal the Arrhenius expression for this reaction to be: log(k/M⁻¹ s⁻¹) = (11.1 ± 0.4) − (34.6 ± 3.1)/θ where θ=2.3RT kJ mol⁻¹.

Australia's radical predatory pricing reforms : what business must know

Radical changes to the Trade Practices Act have the potential to affect significantly, the ability of businesses to engage in vigorous price competition. These changes are designed to prohibit what is colloquially referred to as predatory pricing; the practice of a firm temporarily reducing its prices to a level designed to eliminate its competitors so that, free of competition, it can thereafter, lift them to supra-competitive levels. Unfortunately, because of its scope and the ambiguous new concepts it employs, the section has the potential to apply to all forms of vigorous.price competition and creates significant risks for those businesses who.seek to compete with their rivals by systematically, or irregularly, selling at lower prices than they do. This note examines the section's nature and scope and identifies the pitfalls that it presents for such firms.

The influence of polymerization time and dopant concentration on the absorption of microwave radiation in conducting polypyrrole coated textiles

Temperature changes in conducting polypyrrole/para-toluene-2-sulphonic acid (PPy/pTSA) coated nylon textiles due to microwave absorption in the 8–9 GHz and 15–16 GHz frequency ranges were obtained by a thermography station during simultaneous irradiation of the samples. The temperature values are compared and related to the amounts of reflection, transmission and absorption obtained with a non-contact free space transmission technique, indicating a relationship between microwave absorption and temperature increase. Non-conductive samples showed no temperature increase upon irradiation irrespective of frequency range. The maximum temperature difference of around 4 °C in the conducting fabrics relative to ambient temperature was observed in samples having 48% absorption and 26.5 ± 4% reflection. Samples polymerized for 60 or 120 min with a dopant concentration of 0.018 mol/l or polymerized for 180 min with a dopant concentration of 0.009 mol/l yielded optimum absorption levels. As the surface resistivity decreased and the reflection levels increased, the temperature increase upon irradiation reduced.