Studies on the intramolecular cyclizations of bicyclic delta-hydroxynitriles promoted by triflic anhydride

Studies have been conducted to investigate the reactivity of several bicyclic delta-hydroxynitriles with triflic anhydride in dichloromethane. The reactions of the analogues derived from 1-indanone and 1-tetralone lead to annulated enones. These products arise from an initial elimination reaction that generates an alkene, followed by the addition of the carbon-carbon double bond to the activated cyano group. The intramolecular cyclization of the derivative obtained from 1-benzosuberone unexpectedly followed a different path, giving a cyclic imidate as the major product. In this case, the activated cyano group is directly attacked by the hydroxyl group of the starting delta-hydroxynitrile. Theoretical calculations provide a rationale for the observed reactivity pattern. Both the formation of the triflate via its protonated form, its subsequent ionization to the carbocation, and the cyclization of the resulting alkene to the enone become less favorable when the size of the ring increases due to conformational effects. The opposite trend is observed for the competing Pinner-type cyclization to the imidate. An alternative mechanism for the formation of the lactams from the cyclic imidates under acid-catalyzed conditions has also been proposed.     

A concise asymmetric synthesis of torcetrapib

Optically active torcetrapib was synthesized in seven steps from achiral precursors without the need for protecting groups, utilizing an enantioselective aza-Michael reaction to achieve asymmetry.     

Synthesis and catalytic application of chiral 1,1'-Bi-2-naphthol- and biphenanthrol-based pincer complexes: selective allylation of sulfonimines with allyl stannane and allyl trifluoroborate

New easily accessible 1,1'-bi-2-naphthol- (BINOL-) and biphenanthrol-based chiral pincer complex catalysts were prepared for selective (up to 85% enantiomeric excess) allylation of sulfonimines. The chiral pincer complexes were prepared by a flexible modular approach allowing an efficient tuning of the selectivity of the catalysts. By employment of the different enantiomeric forms of the catalysts, both enantiomers of the homoallylic amines could be selectively obtained. Both allyl stannanes and allyl trifluoroborates can be employed as allyl sources in the reactions. The biphenanthrol-based complexes gave higher selectivity than the substituted BINOL-based analogues, probably because of the well-shaped chiral pocket generated by employment of the biphenanthrol complexes. The enantioselective allylation of sulfonimines presented in this study has important implications for the mechanism given for the pincer complex-catalyzed allylation reactions, confirming that this process takes place without involvement of palladium(0) species.     

Remote hydroxylation of methyl groups by regioselective cyclopalladation. Partial synthesis of hyptatic acid-A

Hyptatic acid-A (32), a 2alpha,3beta,24-trihydroxyolean-12-en-28-oic acid, previously isolated from Hyptis capitata, was obtained from maslinic acid (2). The regioselective cyclopalladation of the axial methyl group on C-4 of maslinic acid afforded the C-24 hydroxymethylene group due to the presence of a C-2-OR substituent. Nevertheless, hederagenin (7) (23-hydroxy derivative) was formed when this oxygenated group was not present.     

Infusion mass spectrometry as a fingerprint to characterize varnishes in oil pictorial artworks

Mass spectrometry methodology to characterize drying oil used as binding media and varnishes in pictorial artworks, prior to conservation or restoration treatment, is proposed. The analytical treatment requires prior basic hydrolysis of the samples to release the fatty acids: caprylic, pelargonic, capric, sebacic, azelaic, suberic, eicosanoic, lauric, mirystic, palmitic, linolenic, linoleic, oleic and stearic, followed by separation from the matrix by a hexane/water extraction. After removing the solvent, the remaining solid is dissolved in potassium hydroxide, propanol and methanol. The mixture is directly infused into a mass spectrometer without any previous derivatization or separation steps. The detector is operated in electrospray negative ion mode and the [M-H](-) ions of the fatty acids enable identification of the acids. Obtained data for fatty acid ion abundances are analyzed by linear discriminant analysis. The drying oils studied (linseed, poppy seed and walnut) were satisfactorily distinguished. The analytical method shows adequate sensitivity, reproducibility, speed and ease. The proposed methodology has been successfully applied to samples from artistic samples belonging to the Cultural Heritage of Valencia (Spain).     

Oxidation of 2-propanol and cyclohexane by the reagent "hydrogen peroxide-vanadate anion-pyrazine-2-carboxylic acid": kinetics and mechanism

The vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA [identical with] pcaH) efficiently catalyzes the oxidation of 2-propanol by hydrogen peroxide to give acetone. UV-vis spectroscopic monitoring of the reaction as well as the kinetics lead to the conclusion that the crucial step of the process is the monomolecular decomposition of a diperoxovanadium(V) complex containing the pca ligand to afford the peroxyl radical, HOO(.-) and a V(IV) derivative. The rate-limiting step in the overall process may not be this (rapid) decomposition itself but (prior to this step) the slow hydrogen transfer from a coordinated H2O2 molecule to the oxygen atom of a pca ligand at the vanadium center: "(pca)(O=)V...O2H2" --> "(pca)(HO-)V-OOH". The V(IV) derivative reacts with a new hydrogen peroxide molecule to generate the hydroxyl radical ("V(IV)" + H2O2 --> "V(V)" + HO(-) + HO(.-)), active in the activation of isopropanol: HO(.-) + Me2CH(OH) --> H2O + Me2C(.-)(OH). The reaction with an alkane, RH, in acetonitrile proceeds analogously, and in this case the hydroxyl radical abstracts a hydrogen atom from the alkane: HO(.-) + RH --> H2O + R(.-). These conclusions are in a good agreement with the results obtained by Bell and co-workers (Khaliullin, R. Z.; Bell, A. T.; Head-Gordon, M. J. Phys. Chem. B 2005, 109, 17984-17992) who recently carried out a density functional theory study of the mechanism of radical generation in the reagent under discussion in acetonitrile.     

Theoretical study of the fragmentation pathways of norbornane in its doubly ionized ground state

The potential energy surface of norbornane in its dicationic singlet ground state has been investigated in detail using density functional theory along with the nonlocal hybrid and gradient-corrected Becke three-parameter Lee-Yang-Parr functional (B3LYP) and the cc-pVDZ basis set. For the sake of more quantitative insight into the chemical reactions induced by double ionization of norbornane, this study was supplemented by a calculation of basic thermodynamic state functions coupled to a focal point analysis of energy differences obtained using correlation treatments and basis sets of improving quality, enabling an extrapolation of these energy differences at the CCSD(T) level in the limit of an asymptotically complete (cc-pV infinity Z) basis set. Our results demonstrate the likelihood of an ultrafast intramolecular rearrangement of the saturated hydrocarbon cage after a sudden removal of two electrons into a kinetically metastable five-membered cyclic C5H8+-CH+-CH3 intermediate, prior to a Coulomb explosion into C5H7+=CH2 and CH3+ fragments, which might explain a tremendous rise of electron-impact (e, 2e) ionization cross sections at electron binding energies around the double-ionization threshold. The first step is straightforward and strongly exothermic (DeltaH298 = -114.0 kcal mol-1). The second step is also exothermic (DeltaH298 = -10.2 kcal mol-1) but requires an activation enthalpy (DeltaH298) of 39.7 kcal/mol. The various factors governing the structure of this intermediate, such as electrostatic interactions, inductive effects, cyclic strains, and methylenic hyperconjugation interactions, are discussed in detail.     

Oxygen barrier properties of organic montmorillonite modified polyamide 11/Poly (vinyl alcohol) films

Organic montmorillonite (OMMT) nano‐platelets were exfoliated and well dispersed in fully bio‐based polyamide 11/Poly(vinyl alcohol) (PA11/PVA) blends. Significantly lower oxygen permeation rates (OTR) were detected for the PA11_72.5PVA_27.5OMMT_x films than those of PA11 and PA11_72.5PVA_27.5 films. An extremely low OTR of 0.218 cm³/m²·day·atm was found for PA11_72.5PVA_27.5OMMT₁ film modified with 1 PHR optimum concentration of well dispersed OMMT nano‐platelets. Similarly, the free volume characteristics evaluated for PA11_72.5PVA_27.5OMMT_x film series reduced to a minimum as the OMMT concentration reached the optimum value. As revealed by dynamic mechanical and differential scanning calorimetric analyses of PA11_72.5PVA_27.5OMMT_x film series, all dynamic glass transition temperature (T_g), melting temperature (T_m) and percentage crystallinity (W_c) values of PA11_72.5PVA_27.5OMMT_x films were noticeably higher than those of PA11_72.5PVA_27.5 film without addition of OMMT. In fact, T_gs, T_ms and W_cs evaluated for PA11_72.5PVA_27.5OMMT_x films increased to a maximum, as their OMMT reached the optimum concentration. The considerably enhanced oxygen barrier resistance found for PA11_72.5PVA_27.5OMMT_x films was ascribed to the considerably reduced free volume characteristics and much longer permeation path caused by impermeably OMMT nano‐platelets well dispersed in PA11_72.5PVA_27.5OMMT_x films.     

Aharonov-Bohm conductance modulation in ballistic carbon nanotubes

We report on magnetoconductance experiments in ballistic multiwalled carbon nanotubes threaded by magnetic fields as large as 55 T. In the high temperature regime (100 K), giant modulations of the conductance, mediated by the Fermi level location, are unveiled. The experimental data are consistently analyzed in terms of the field-dependent density of states of the external shell that modulates the injection properties at the electrode-nanotube interface, and the resulting linear conductance. This is the first unambiguous experimental evidence of Aharonov-Bohm effect in clean multiwalled carbon nanotubes.     

Low-power bacteriorhodopsin-silicon n-channel metal-oxide field-effect transistor photoreceiver

A bacteriorhodopsin (bR)-silicon n-channel metal-oxide field-effect transistor (NMOSFET) monolithically integrated photoreceiver is demonstrated. The bR film is selectively formed on an external gate electrode of the transistor by electrophoretic deposition. A modified biasing circuit is incorporated, which helps to match the resistance of the bR film to the input impedance of the NMOSFET and to shift the operating point of the transistor to coincide with the maximum gain. The photoreceiver exhibits a responsivity of 4.7 mA/W.