The soft nucleophilicity of organotellurolates driving the S(N)2-type lactone ring-opening reaction

Lithium and magnesium organotellurolates were reacted with lactones producing the corresponding tellurocarboxylic acids. Treatment of the reaction mixture with lithium aluminum hydride allowed the isolation of the corresponding hydroxytellurides in a one-pot operation. (C) 2009 Published by Elsevier Ltd

Practical synthesis of chiral beta-telluro amines by ring-opening reaction of aziridines

A set of chiral beta-tellurium amines and their selenium and sulfur-containing derivatives have been efficiently synthesized in good to excellent yields via the ring-opening reaction of chiral aziridines by chalcogen nucleophilic species. (C) 2008 Elsevier B.V. All rights reserved.

Iodine(III)-promoted ring expansion of 1-vinylcycloalkanol derivatives: A metal-free approach toward seven-membered rings

A versatile and metal-free approach for the synthesis of molecules bearing seven- and eight-membered rings is described. The strategy is based on the ring expansion of 1-vinylcycloalkanols (or the corresponding silyl or methyl ether) mediated by the hypervalent iodine reagent HTIB (Phl(OH)OTs). The reaction condition can be easily adjusted to give seven-membered rings bearing different functional groups. A route to medium-ring lactones was also developed.

Ring Contraction of 1,2-Dihydronaphthalenes Promoted by Thallium(III) in Acetonitrile: A Diastereoselective Approach to Indanes

trans-1,3-Disubstituted indanes are conveniently accessed by a stereoselective ring contraction of 1,2-dihydronaphthalenes upon treatment with thallium(III) nitrate (TTN) in acetonitrile. Under these conditions, the oxidative rearrangement of either di- or trisubstituted double bonds is possible.

A Diastereoselective Total Synthesis of trans-Trikentrin A: A Ring Contraction Approach

A new route to obtain the polyalkylated indole (+/-)-trans-trikentrin A was developed. The synthesis of this natural alkaloid features a thallium(III)mediated ring contraction reaction to obtain the trans-1,3-disubstituted five-membered ring in a diastereoselective manner. Thallium(III) is chemoselective in this rearrangement, reacting with the olefin without oxidation of the indole moiety. Other key transformations are the Bartoli`s reaction to construct the heterocyclic ring and a Heck coupling to add the carbons atom that will originate the nonaromatic cycle.

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.

An epoxide ring-opening approach for a short and stereoselective synthesis of icetexane diterpenoids

A new approach for the synthesis of the core skeleton of icetexane diterpenoids is presented and deals with an epoxide ring-opening reaction by metallated aromatic compounds. Employing this strategy, a short synthesis of an icetexane analogue of brussonol was achieved in just four steps from 2-allyl-cyclohexanone. (C) 2009 Elsevier Ltd. All rights reserved.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Thomas-Fermi ground state of dipolar fermions in a circular storage ring

Recent developments in the field of ultracold gases has led to the production of degenerate samples of polar molecules. These have large static electric-dipole moments, which in turn causes the molecules to interact strongly. We investigate the interaction of polar particles in waveguide geometries subject to an applied polarizing field. For circular waveguides, tilting the direction of the polarizing field creates a periodic inhomogeneity of the interparticle interaction. We explore the consequences of geometry and interaction for stability of the ground state within the Thomas-Fermi model. Certain combinations of tilt angles and interaction strengths are found to preclude the existence of a stable Thomas-Fermi ground state. The system is shown to exhibit different behavior for quasi-one-dimensional and three-dimensional trapping geometries.

Superconducting state in a mesoscopic segment ring

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Aharonov-Bohm oscillations in a quantum ring: Eccentricity and electric-field effects

The effects of an in-plane electric field and eccentricity on the electronic spectrum of a GaAs quantum ring in a perpendicular magnetic field are studied. The effective-mass equation is solved by two different methods: an adiabatic approximation and a diagonalization procedure after a conformal mapping. It is shown that the electric field and the eccentricity may suppress the Aharonov-Bohm oscillations of the lower energy levels. Simple expressions for the threshold energy and the number of flat energy bands are found. In the case of a thin and eccentric ring, the intensity of a critical field which compensates the main effects of eccentricity is determined. The energy spectra are found in qualitative agreement with previous experimental and theoretical works on anisotropic rings.

Dynamical evolution of Saturn's F ring dust particles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Orbital evolution of the mu and nu dust ring particles of Uranus

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Geologia, Geocronologia, Geoquímica e Petrogênese das Rochas Ígneas Cretácicas da Província Magmática do Cabo e suas Relações com as Unidades Sedimentares da Bacia de Pernambuco (NE do Brasil)

The area studied forms a thin NNE-directed belt situated south of Recife town (Pernambuco state), northeastern Brazil. Geologically, it comprises the Pernambuco Basin (PB), which is limited by the Pernambuco Lineament to the north, the Maragogi high to the south and the Pernambuco Alagoas massif to the west, all of them with Precambrian age. This thesis reports the results obtained for the Cabo Magmatic Province (CMP), aiming the characterization of the geology, stratigraphy, geochronology, geochemistry and petrogenesis of the Cretaceous igneous rocks presented in the PB. The PB is composed of the Cabo Formation (rift phase) at the base (polymictic conglomerates, sandstones, shales), an intermediate unit, the Estiva Formation (marbles and argillites), and, at the top, the Algodoais Formation (monomictic conglomerates, sandstones, shales). The CMP is represented by trachytes, rhyolites, pyroclastics (ignimbrites), basalts / trachy-andesites, monzonites and alkali-feldspar granite, which occur as dykes, flows, sills, laccoliths and plugs. Field observations and well descriptions show that the majority of the magmatic rocks have intrusive contacts with the Cabo Formation, although some occurrences are also suggestive of synchronism between volcanism and siliciclastic sedimentation. 40Ar/39Ar and zircon fission tracks for the magmatic rocks indicate an average age of 102 r 1 Ma for the CMP. This age represents an expressive event in the province and is detected in all igneous dated materials. It is considered as a minimum age (Albian) for the magmatic episode and the peak of the rift phase in the PB. The 40Ar/39Ar dates are about 10-14 Ma younger than published palynologic ages for this basin. Geochemically, the CMP may be divided in two major groups; i) a transitional to alkaline suite, constituted by basalts to trachy-andesites (types with fine-grained textures and phenocrysts of sanidine and plagioclase), trachytes (porphyrytic texture, with phenocrysts of sanidine and plagioclase) and monzonites; ii) a alkaline suite, highly fractionated, acidic volcano-plutonic association, formed by four subtypes (pyroclastic flows ignimbrites, fine-to medium-grained rhyolites, a high level granite, and later rhyolites). These four types are distinguished essentially by field aspects and petrographic and textural features. Compatible versus incompatible trace element concentrations and geochemical modeling based on both major and trace elements suggest the evolution through low pressure fractional crystallization for trachytes and other acidic rocks, whereas basalts / trachy-andesites and monzonites evolved by partial melting from a mantle source. Sr and Nd isotopes reveal two distinct sources for the rocks of the CMP. Concerning the acidic ones, the high initial Sr ratios (ISr = 0.7064-1.2295) and the negative HNd (-0.43 to -3.67) indicate a crustal source with mesoproterozoic model ages (TDM from 0.92 to 1.04 Ga). On the other hand, the basic to intermediate rocks have low ISr (0.7031-0.7042) and positive HNd (+1.28 to +1.98), which requires the depleted mantle as the most probable source; their model ages are in the range 0.61-0.66 Ga. However, the light rare earth enrichment of these rocks and partial melting modeling point to an incompatible-enriched lherzolitic mantle with very low quantity of garnet (1-3%). This apparent difference between geochemical and Nd isotopes may be resolved by assuming that the metasomatizing agent did not obliterate the original isotopic characteristics of the magmas. A 2 to 5% partial melting of this mantle at approximately 14 kbar and 1269oC account very well the basalts and trachy-andesites studied. By using these pressure and temperatures estimates for the generation of the basaltic to trachy-andesitic magma, it is determined a lithospheric stretching (E) of 2.5. This E value is an appropriated estimate for the sub-crustal stretching (astenospheric or the base of the lithosphere?) region under the Pernambuco Basin, the crustal stretching probably being lower. The integration of all data obtained in this thesis permits to interpret the magmatic evolution of the PB as follows; 1st) the partial melting of a garnet-bearing lherzolite generates incompatible-enriched basaltic, trachy-andesitic and monzonitic magmas; 2nd) the underplating of these basaltic magmas at the base of the continental crust triggers the partial melting of this crust, and thus originating the acidic magmas; 3rd) concomitantly with the previous stage, trachytic magmas were produced by fractionation from a monzonitic to trachy-andesitic liquid; 4th) the emplacement of the several magmas in superficial (e.g. flows) or sub-superficial (e.g. dykes, sills, domes, laccoliths) depths was almost synchronically, at about 102 r 1 Ma, and usually crosscutting the sedimentary rocks of the Cabo Formation. The presence of garnet in the lherzolitic mantle does not agree with pressures of about 14 kbar for the generation of the basaltic magma, as calculated based on chemical parameters. This can be resolved by admitting the astenospheric uplifting under the rift, which would place deep and hot material (mantle plume?) at sub-crustal depths. The generation of the magmas and their subsequent emplacement would be coupled with the crustal rifting of the PB, the border (NNE-SSW directed) and transfer (NW-SE directed) faults serving as conduits for the magma emplacement. Based on the E parameter and the integration of 40Ar/39Ar and palynologic data it is interpreted a maximum duration of 10-14 Ma for the rift phase (Cabo Formation clastic sedimentation and basic to acidic magmatism) of the PB

Petrologia do magmatismo tardi-brasiliano no Maciço São José de Campestre(RN/PB), com ênfase no Plúton Alcalino Caxexa

The area studied is located on the north-easternmost portion of the Borborema Province, on the so-called São José de Campestre Massif, States of RN and PB, Northeast Brazil. Field relations and petrographic, geochemical and isotope data permitted the separation of five suites of plutonic rocks: alkali-feldspar granite (Caxexa Pluton), which constitutes the main subject of this dissertation, amphibole-biotite granite (Cabeçudo Pluton), biotite microgranite, gabbronorite to monzonite (Basic to Intermediate Suite) and aluminous granitoid. The Caxexa Pluton is laterally associated to the Remígio Pocinhos Shear Zone, with its emplacement along the mylonitic contact between the gneissic basement and the micashists. This pluton corresponds to a syntectonic intrusion elongated in the N-S direction, with about 50 km2 of outcropping surface. It is composed exclusively of alkali-feldspar granites, having clinopyroxene (aegirine-augite and hedenbergite), andradite-rich garnet, sphene and magnetite. It is classified geochemically as high silica rocks (>70 % wt), metaluminous to slightly peraluminous (normative corindon < 1%), with high total alkalis (>10% wt), Sr, iron number (#Fe=90-98) and agpaitic index (0.86-1.00), and positive europium anomaly. The Cabeçudo Pluton is composed of porphyritic rocks, commonly containing basic to intermediate magmatic enclaves often with mingling and mixing textures. Petrographically, it presents k-feldspar and plagioclase phenocrysts as the essential minerals, besides the accessories amphibole, biotite, sphene and magnetite. It is metaluminous and shows characteristics transitional between the calc-alkaline and alkaline series (or monzonitic subalkaline). Its REE content is greater than those ones of the Caxexa Pluton and biotite microgranite, and all spectra have negative europium anomalies. The biotite microgranites occur mainly on the central and eastern portion of the mapped area, as dykes and sheets with decimetric thickness, hosted principally in orthogneisses and micashists. Their field relationships as regards the Caxexa and Cabeçudo plutons suggested that they are late-tectonic intrusions. They are typically biotite granites, having also sphene, amphibole, allanite, opaques and zircon in the accessory assemblage. Geochemically they can be distinguished from the porphyritic types because the biotite microgranites are more evolved, peraluminous, and have more fractionated REE spectra. The Basic to Intermediate rocks form a volumetrically expressive elliptical, kilometric scale body on the Southeast, as well as sheets in micashists. They are classified as gabbronorites to monzonites, with the two pyroxenes and biotite, besides subordinated amounts of amphibole, sphene, ilmenite and allanite. These rocks do not show a well-defined geochemical trend, however they may possibly represent a monzonitic (shoshonitic) series. Their REE spectra have negative europium anomalies and REE contents greater than the other suites. The aluminous granitoids are volumetrically restricted, and have been observed in close association with migmatised micashists bordering the gabbronorite pluton. They are composed of almandine-rich garnet, andalusite, biotite and muscovite, and are akin to the peraluminous suites. Rb-Sr (whole rock) and Sm-Nd (whole-rock and mineral) isotopes furnished a minimum estimate of the crystallization (578±14 Ma) and the final resetting age of the Rb-Sr system (536±4 Ma) in the Caxexa Pluton. The aluminous granitoid has a Sm-Nd garnet age similar to that one of the Caxexa Pluton, that is 574±67 Ma. The strong interaction of shear bands and pegmatite dykes favoured the opening of the Rb-Sr system for the Caxexa Pluton and biotite microgranite. The amphibole-plagioclase geothermometer and the Al-in amphibole geobarometer indicate minimum conditions of 560°C and 7 kbar for the Cabeçudo Pluton, 730°C and 6 kbar for the microgranite and 743°C and 5 kbar for the basic to intermediate suite. The Zr saturation geothermometer reveals temperatures of respectively 855°C, 812°C and 957°C for those suites, whereas the Caxexa Pluton shows temperatures of around 757°C. The Caxexa, Cabeçudo and microgranites suites crystallized under high fO2 (presence of magnetite). On the other hand, the occurrence of ilmenite suggests less oxidant conditions in the basic to intermediate suite. Field relations demonstrate the intrusive character of the granitoids into a tectonically relatively stable continental crust. This is corroborated by petrographic and geochemical data, which suggest a late- or post-collisional tectonic context. It follows that the generation and emplacement of those granitoid suites is related to the latest events of the Brasiliano orogeny. Finally, the relationships between eNd (600 Ma), TDM (Nd) and initial Sr isotope ratio (ISr) do not permit to define the precise sources of the granitoids. Nevertheless, trace element modelling and isotopic comparisons suggest the participation of the metasomatised mantle in the generation of these suites, probably modified by different degrees of crustal contamination. In this way, a metasomatised mantle would not be a particular characteristic of the Neoproterozoic lithosphere, but a remarkable feature of this portion of the Borborema Province since Archaean and Paleoproterozoic times.