Stereoselective Nucleophilic Addition of Potassium Alkyltrifluoroborates to Cyclic N-Acyliminium Ions: a Simple and Mild Approach to Chiral 5-Alkyl-pyrrolidin-2-ones

The stereoselective nucleophilic addition of potassium alkyltrifluoroborates to cyclic N-acyliminium ions derived from N-benzyl-3,4,5-triacetoxy-pyrrolidin-2-one, which affords 5-substituted-pyrrolidin-2-ones, is described. The products are obtained in moderate to good yields and are produced predominantly as the anti diastereomer.

Chemoselective screening for the reduction of a chiral functionalised (+/-)-2-(phenylthio)cyclohexanone by whole cells of Brazilian micro-organisms

The use of whole cells of micro-organisms to bring about the biotransformation of an organic compound offers a number of advantages, but problems caused by enzymatic Promiscuity may be encountered upon With Substrates hearing more than one functional group. A one-pot screening method, in which whole fungal cells were incubated with a Mixture of 4-rnethylcyclohexanone I and phenyl methyl Sulfide 2, has been employed to determine the chemoselectivity of various biocatalysts. The hyphomycetes, Aspergillus terreus CCT 3320 and A. terreus URM 3571, catalysed the oxidation of 2 accompanied by the reduction of I to 4-methylcyclohexanol 1a and, for strain A. terreus CCT 3320, the Baeyer-Villiger oxidation of 1. The Basidomycetes, Trametes versicolor CCB 202, Pycnoporus sanguineus CCB 501 and Trichaptum byssogenum CCB 203, catalysed the oxidation of 2 and the reduction 1, but no Baeyer-Villiger reaction products were detected. In contrast. Trametes rigida CCB 285 catalysed the biotransformation of 1 to 1a, exclusively, in the absence of any detectable Sulfide oxidation reactions. The chemoselective reduction Of (+/-)-2-(phenylthio)cyclohexanone 3 by T. rigida CCB 285 afforded exclusively the (+)-cis-(1R,2S) and (+)-trans-(1S,2S) diastereoisomers of 2-(phenylthio)cyclohexan-1-ol 3a in moderate yields (13% and 27%, respectively) and high enantiomeric excesses (>98%). Chemoselective screening for the reduction of a ketone and/or the oxidation Of a Sulfide group in one pot by whole cells of micro-organisms represents an attractive technique with applications in the development of synthesis of complex molecule hearing different functional groups. (C) 2008 Published by Elsevier Ltd.

New insights on surface-enhanced Raman scattering based on controlled aggregation and spectroscopic studies, DFT calculations and symmetry analysis for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine adsorbed onto citrate-stabilized gold nanoparticles

Asystematic study on the surface-enhanced Raman scattering (SERS) for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine (bptz) adsorbed onto citrate-modified gold nanoparticles (cit-AuNps) was carried out based on electronic and vibrational spectroscopy and density functional methods. The citrate/bptz exchange was carefully controlled by the stepwise addition of bptz to the cit-AuNps, inducing flocculation and leading to the rise of a characteristic plasmon coupling band in the visible region. Such stepwise procedure led to a uniform decrease of the citrate SERS signals and to the rise of characteristic peaks of bptz, consistent with surface binding via the N heterocyclic atoms. In contrast, single addition of a large amount of bptz promoted complete aggregation of the nanoparticles, leading to a strong enhancement of the SERS signals. In this case, from the distinct Raman profiles involved, the formation of a new SERS environment became apparent, conjugating the influence of the local hot spots and charge-transfer (CT) effects. The most strongly enhanced vibrations belong to a(1) and b(2) representations, and were interpreted in terms of the electromagnetic and the CT mechanisms: the latter involving significant contribution of vibronic coupling in the system. Copyright (C) 2010 John Wiley & Sons, Ltd.

Mild and efficient one-pot synthesis of chiral beta-chalcogen amides via 2-oxazoline ring-opening reaction mediated by indium metal

A simple and efficient procedure for the synthesis of beta-seleno and beta-thio amides via the ring-opening reaction of chiral 2-oxazolines in the presence of indium metal has been developed. Features of this method include the following: (i) easily and accessible starting materials; (ii) indium metal is more stable and less expensive then its respective salts; (iii) useful to excellent yields of beta-chalcogen amides derivatives. (C) 2008 Elsevier B. V. All rights reserved.

Synthesis and application of chiral beta-amino disulfides as ligands for the enantioselective addition of diethylzinc to aldehydes

A new class of chiral beta-amino disulfides was synthesized from readily available and inexpensive starting materials by a straightforward method and their abilities as ligands were examined in the enantioselective addition of diethylzinc to aldehydes. Enantiomeric excesses of up to 99% have been obtained using 0.5 mol % of the chiral catalysts.

Stereoselective synthesis of azetidine-derived glutamate and aspartate analogues from chiral azetidin-3-ones

The stereoselective syntheses of cis conformationally constrained glutamate and aspartate analogues, containing an azetidine framework were accomplished from (S)-N-tosyl-2-phenylglycine in moderate overall yields. The key steps in these syntheses involved an efficient Wittig olefination of an azetidin-3-one, followed by a highly stereoselective rhodium catalyzed hydrogenation. The route could also be applied to the synthesis of a trans glutamate analogue, since epimerization of cis to trans isomer could be performed using DBU in toluene at reflux. (C) 2008 Elsevier Ltd. All rights reserved.

Kinetic resolution of iodophenylethanols by Candida antarctica lipase and their application for the synthesis of chiral biphenyl compounds

The kinetic resolution of (+/-)-iodophenylethanols was carried out using lipase from Candida antarctica and in some cases the enantiomeric excesses were high (up to >98%). Enantiomerically enriched (S)-iodophenylethanols produced by the enzymatic resolution process were used in the synthesis of chiral biphenyl compounds by the Suzuki reaction with good yields (63-65%). (C) 2010 Elsevier Ltd. All rights reserved.

Multimilligram enantioresolution of sulfoxide proton pump inhibitors by liquid chromatography on polysaccharide-based chiral stationary phase

The enantiomers of sulfoxide proton pump inhibitors - omeprazole, lansoprazole, rabeprazole and Ro 18-5364 - were enantiomerically separated by liquid chromatography at multimilligram scale on a poly saccharide-based chiral stationary phase using normal and polar organic conditions as mobile phase. The values of the recovery and production rate were significant for each enantiomer; better results were achieved using a solid-phase injection system. However, this system was applied just for the enantionteric separation of omeprazole to demonstrate the applicability of this injection mode at milligram scale. The chiroptical characterization of the compounds was performed using a polarimeter and a circular dichroism detector. The higher enantiomeric purity obtained for the isolated enantiomers suggests that the methods here described should be considered as a simple and rapid way to obtain enantiomeric pure standards for analytical purpose. (C) 2007 Elsevier B.V. All rights reserved.

Hamiltonian constraint analysis of vector field theories with spontaneous Lorentz symmetry breaking

Recent investigations of various quantum-gravity theories have revealed a variety of possible mechanisms that lead to Lorentz violation. One of the more elegant of these mechanisms is known as Spontaneous Lorentz Symmetry Breaking (SLSB), where a vector or tensor field acquires a nonzero vacuum expectation value. As a consequence of this symmetry breaking, massless Nambu-Goldstone modes appear with properties similar to the photon in Electromagnetism. This thesis considers the most general class of vector field theories that exhibit spontaneous Lorentz violation-known as bumblebee models-and examines their candidacy as potential alternative explanations of E&M, offering the possibility that Einstein-Maxwell theory could emerge as a result of SLSB rather than of local U(1) gauge invariance. With this aim we employ Dirac's Hamiltonian Constraint Analysis procedure to examine the constraint structures and degrees of freedom inherent in three candidate bumblebee models, each with a different potential function, and compare these results to those of Electromagnetism. We find that none of these models share similar constraint structures to that of E&M, and that the number of degrees of freedom for each model exceeds that of Electromagnetism by at least two, pointing to the potential existence of massive modes or propagating ghost modes in the bumblebee theories.

A PRELIMINARY HABITAT SUITABILITY ANALYSIS FOR THE RESTORATION OF SOUTH CHINA TIGERS IN THE HUPINGSHAN RESERVE, CHINA

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A Preliminary Habitat Suitability Analysis for the Restoration of South China Tigers in the Hupingshan Reserve, China

The South China tiger, Panthera tigris amoyensis, once roamed the greater part of southern China. However, expanding human populations and other anthropogenic effects have resulted in the extinction of the wild population. The Chinese government has expressed interest in a reintroduction program for this species of tigers. Recent studies suggest that the Hupingshan preserve is potentially a good candidate for a tiger reintroduction program. Hupingshan is located on the border of the Hunan and Hubei provinces in Southern China. This study was a preliminary habitat suitability analysis, for the restoration of South China tigers in the Hupingshan reserve, China. ArcGIS 9.0 was used to develop a model that combined roads, railroads, slope, land cover, park classification, and population density. The tiger habitat suitability analysis was performed by weighting and combining the various layers. Preliminary results suggest that the Hupingshan reserve is suitable habitat for the reintroduction of South China tigers.

Efeitos de ordenamento chiral em supercondutores e sistemas magnéticos desordenados

Este trabalho apresenta uma investigação experimental sobre as propriedades magnéticas e de transporte elétrico de sistemas caracterizados por desordem e frustração. Tais sistemas são amostras granulares do supercondutor de alta temperatura crítica YBa2Cu3O7-δ e amostras do tipo vidro-de-spin e reentrantes das ligas magnéticas diluídas AuMn 8at% e AuFe xat% (x = 8, 12, 15, 18 e 21). No supercondutor granular foram estudados os efeitos de flutuações termodinâmicas na magnetocondutividade nas proximidades da transição supercondutora e a linha de irreversibilidades magnéticas. A transição para o estado de resistência nula é um processo que ocorre em duas etapas. Inicialmente, a transição de pareamento estabiliza a supercondutividade no interior dos grãos. A transição de coerência ocorre em temperaturas inferiores e ativa ligações fracas entre os grãos através de um processo do tipo percolação. O regime que antecede a transição de coerência é caracterizado por flutuações na fase do parâmetro de ordem. A linha de irreversibilidades magnéticas, estudada a partir da magnetoresistência e magnetização DC, revela um comportamento do tipo Almeida-Thouless em baixos campos magnéticos aplicados, seguido de um crossover, em µ0H = 0.1 T, para um comportamento do tipo Gabay-Toulouse. A linha de irreversibilidades é interpretada como sendo uma manifestação experimental de uma transição de vidro chiral. As ligas magnéticas diluídas foram estudadas através do efeito Hall extraordinário. Os resultados mostram claramente que dois termos de sinais contrários contribuem para este efeito nestes sistemas. Em particular, é observada uma anomalia no coeficiente de Hall extraordinário em temperaturas próximas à temperatura de ordenamento dos vidros-de-spin e de “canting” dos reentrantes que não é prevista por nenhuma teoria convencional de efeito Hall. A interpretação dos resultados é feita em termos do modelo de vidro chiral, mostrando a importância de uma contribuição de origem puramente chiral. Esta é a primeira vez que a chiralidade, uma propriedade intrínseca de sistemas desordenados e frustrados, é observada experimentalmente de modo direto.

Calculable lepton masses, seesaw relations, and four neutrino mixings in a 3-3-1 model with an extra U(1) symmetry

We propose a scheme in which the masses of the heavier leptons obey seesaw type relations. The light lepton masses, except the electron and the electron neutrino ones, are generated by one loop level radiative corrections. We work in a version of the 3-3-1 electroweak model that predicts singlets (charged and neutral) of heavy leptons beyond the known ones. An extra U(1)(Omega) symmetry is introduced in order to avoid the light leptons getting masses at the tree level. The electron mass induces an explicit symmetry breaking at U(1)(Omega). We discuss also the mixing matrix among four neutrinos. The new energy scale required is not higher than a few TeV.