Steric effects on alkyl cation affinities of maingroup-element hydrides

We have carried out an extensive exploration of gas‐phase alkyl cation affinities (ACA) of archetypal anionic and neutral bases across the periodic system using zeroth order regular approximation‐relativistic density functional theory at BP86/QZ4P//BP86/TZ2P. ACA values were computed for the methyl, ethyl, i‐propyl and t‐butyl cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K ACA of all anionic (XH) and neutral bases (XH_n) constituted by maingroup‐element hydrides of groups 14–17 and the noble gases (group 18) along the periods 1–6. Another purpose is to determine and rationalize the trend in affinity for a cation as the latter varies from proton to t‐butyl cation. This undertaking is supported by quantitative bond energy decomposition analyses. Correlations are established between PA and ACA values. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011     

Recent developments and perspectives in palladium-catalyzed cyanation of aryl halides: synthesis of benzonitriles

The palladium-catalyzed cyanation of Ar-X (X = I, Br, Cl, OTf, and H) allows for an efficient access towards benzonitriles. After its discovery in 1973 and following significant improvements in recent decades, this methodology has become nowadays the most popular for preparation of substituted aromatic nitriles. In this critical review, we summarize the important developments in this area from 2000 until 2010 (151 references).     

Directing alkyl chain ordering of functional phosphorus coupling agents on ZrO2

ZrO(2) powder (6.6 m(2)/g) was modified using polymerizable phosphorus-based coupling agents (P-CAs) (i.e., phosphonic acid, phosphoric acid, and bis-phosphonic acid), resulting in densely grafted layers as determined by thermogravimetry and elemental analysis (up to 4.2 molecules/nm(2)). The applied P-CAs contained a methacrylate group, which led to the covalent incorporation of a polymerizable moiety into the grafted layer. To direct the ordering of the alkyl chains in the layer, three different approaches were evaluated with respect to their structure-directing ability by means of FT-IR and nitrogen sorption at 77 K: (i) variation of the chain length, (ii) variation of the anchoring group and (iii) comodification with a defined amount of a nonfunctional phosphonic acid (variation of the functional/nonfunctional acid ratio). It was shown that the chain length and anchoring group size have significant effects on the alkyl chain ordering and morphology of the layer.     

Biotechnological Production of 20-alpha-Dihydrodydrogesterone at Pilot Scale

The human sex hormone progesterone plays an essential and complex role in a number of physiological processes. Progesterone deficiency is associated with menstrual disorders and infertility as well as premature birth and abortion. For progesterone replacement therapy, the synthetic progestogen dydrogesterone is commonly used. In the body, this drug is metabolized to 20α-dihydrodydrogesterone (20α-DHD), which also shows extensive pharmacological effects and hence could act as a therapeutic agent itself. In this study, we describe an efficient biotechnological production procedure for 20α-DHD that employs the stereo- and regioselective reduction of dydrogesterone in a whole-cell biotransformation process based on recombinant fission yeast cells expressing the human enzyme AKR1C1 (20α-hydroxysteroid dehydrogenase, 20α-HSD). In a fed-batch fermentation at pilot scale (70 L) with a genetically improved production strain and under optimized reaction conditions, an average 20α-DHD production rate of 190 μM day⁻¹ was determined for a total biotransformation time of 136 h. Combined with an effective and reliable downstream processing, a continuous production rate of 12.3 ± 1.4 g 20α-DHD per week and fermenter was achieved. We thus established an AKR-dependent whole-cell biotransformation process that can also be used for the production of other AKR1C1 substrates (as exemplarily shown by the production of 20α-dihydroprogesterone in gram scale) and is in principle suited for the production of further human AKR metabolites at industrial scale.     

Unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes as versatile building blocks for boron-doped π-conjugated systems

The targeted hydrolysis of the 9,10-dihydro-9,10-diboraanthracene adduct (Me(2)S)HB(C(6)H(4))(2)BH(SMe(2)) (1) with 0.5 equiv of H(2)O leads to formation of the borinic acid anhydride [(Me(2)S)HB(C(6)H(4))(2)B](2)O (2) and thereby provides access to the field of unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes. Compound 2 reacts with tBuC≡CH to give the corresponding vinyl derivative in an essentially quantitative conversion. Subsequent cleavage of the B-O-B bridge by LiAlH(4) with formation of hydridoborate functionalities is possible but is accompanied by partial B-C(vinyl) bond degradation. This situation changes when the related mesityl derivative [MesB(C(6)H(4))(2)B](2)O (7) is employed, which can be synthesized from BrB(C(6)H(4))(2)BBr (6) by treatment with 1 equiv of MesMgBr and subsequent hydrolysis. The reaction of 7 with LiAlH(4) in tetrahydrofuran (THF) furnishes Li[MesB(C(6)H(4))(2)BH(2)] (8); hydride elimination with Me(3)SiCl leads to formation of the THF adduct MesB(C(6)H(4))(2)BH(THF) (9·THF). Alternatively, 7 can be transformed into the bromoborane MesB(C(6)H(4))(2)BBr (10) by treatment with BBr(3). A Br/H-exchange reaction between 10 and Et(3)SiH yields the donor-free borane MesB(C(6)H(4))(2)BH (9), which forms B-H-B bridged dimers (9)(2) in the solid state. The vinyl borane MesB(C(6)H(4))(2)BC(H)=C(H)Mes (14) is accessible from MesC≡CH and either 9·THF or 9. Compared with the related compound Mes(2)BC(H)=C(H)Mes, the electronic absorption and emission spectra of 14 reveal bathochromic shifts of Δλ(abs)=17 nm and Δλ(em)=74 nm, which can be attributed to the rigid, fully delocalized π framework of the [MesB(C(6)H(4))(2)B] chromophore.     

General and selective iron-catalyzed transfer hydrogenation of nitroarenes without base

The first well-defined iron-based catalyst system for the reduction of nitroarenes to anilines has been developed applying formic acid as reducing agent. A broad range of substrates including other reducible functional groups were converted to the corresponding anilines in good to excellent yields at mild conditions. Notably, the process constitutes a rare example of base-free transfer hydrogenations.     

Formation of a mesoscopic skin barrier in mesoglobules of thermoresponsive polymers

With the combination of molecular scale information from electron paramagnetic resonance (EPR) spectroscopy and meso-/macroscopic information from various other characterization techniques, the formation of mesoglobules of thermoresponsive dendronized polymers is explained. Apparent differences in the EPR spectra in dependence of the heating rate, the chemical nature of the dendritic substructure of the polymer, and the concentration are interpreted to be caused by the formation of a dense polymeric layer at the periphery of the mesoglobule. This skin barrier is formed in a narrow temperature range of ~4 K above T(C) and prohibits the release of molecules that are incorporated in the polymer aggregate. In large mesoglobules, formed at low heating rates and at high polymer concentrations, a considerable amount of water is entrapped that microphase-separates from the collapsed polymer chains at high temperatures. This results in the aggregates possessing an aqueous core and a corona consisting of collapsed polymer chains. A fast heating rate, a low polymer concentration, and hydrophobic subunits in the dendritic polymer side chains make the entrapment of water less favorable and lead to a higher degree of vitrification. This may bear consequences for the design and use of thermoresponsive polymeric systems in the fast growing field of drug delivery.     

Spectroscopic properties of lanthanoid benzene carboxylates in the solid state: Part 2. Polar substituted benzoates

Europium and terbium complexes of ortho, meta and para substituted benzoate ligands including nitrobenzoate (NBA), aminobenzoate (ABA), hydroxybenzoate (OHBA) and methoxybenzoate (MeOBA) have been synthesised by metathesis reactions, carried out in aqueous media. The complexes were characterised by elemental, compositional and structural investigations, including microanalysis, EDTA titrations, differential thermal analysis, infra red spectroscopy, X-ray powder diffraction and single crystal structural analyses. Besides this, strong emphasis was on the determination of the optoelectronic properties of the compounds in the solid state. In this regard, reflectance, excitation and emission spectra were recorded. From these, the emission and excitation efficiencies were determined. The relative intensities as well as the splitting patterns of the ⁵D₀ → ⁷F_J transitions in the europium emission spectra are discussed.