Petasis Borono-Mannich reaction and allylation of carbonyl compounds via transient allyl boronates generated by palladium-catalyzed substitution of allyl alcohols. an efficient one-pot route to stereodefined alpha-amino acids and homoallyl alcohols

An efficient one-pot procedure was designed by integration of the pincer-complex-catalyzed borylation of allyl alcohols in the Petasis borono-Mannich reaction and in allylation of aldehydes and ketones. These procedures are suitable for one-pot synthesis of alpha-amino acids and homoallyl alcohols from easily available allyl alcohol, amine, aldehyde, or ketone substrates. In the presented transformations, the active allylating agents are in situ generated allyl boronic acid derivatives. These transient intermediates are proved to be reasonably acid-, base-, alcohol-, water-, and air-stable species, which allows a high level of compatibility with the reaction conditions of the allylation of various aldehyde/ketone and imine electrophiles. The boronate source of the reaction is diboronic acid or in situ hydrolyzed diboronate ester ensuring that the waste product of the reaction is nontoxic boric acid. The regio- and stereoselectivity of the reaction is excellent, as almost all products form as single regio- and stereoisomers. The described procedure is suitable to create quaternary carbon centers in branched allylic products without formation of the corresponding linear allylic isomers. Furthermore, products comprising three stereocenters were formed as single products without formation of other diastereomers. Because of the highly disciplined consecutive processes, up to four-step, four-component transformations could be performed selectively as a one-pot sequence. For example, stereodefined pyroglutamic acid could be prepared from a simple allyl alcohol, a commercially available amine, and glyoxylic acid in a one-step procedure. The presented method also grants an easy access to stereodefined 1,7-dienes that are useful substrates for Grubbs ring-closing metathesis.     

Pressure-temperature phase diagram of the ferromagnetic Kondo lattice compound CeRuPO

The new example of a ferromagnetic Kondo lattice, CeRuPO, is a good candidate which offers the opportunity to investigate the physical properties near a ferromagnetic instability. Macroscopic experiments evidenced a Kondo temperature and Curie temperature of . We have investigated the pressure-temperature phase diagram of CeRuPO by means of electrical resistivity measurements on high quality single crystals in the temperature interval from 1.8 to 300 K. The pressure dependence of the ordering temperature follows the anticipated behavior of a Ce-based Kondo lattice system, where pressure is expected to suppress the magnetic order. The critical pressure for the suppression of the transition temperature to zero is estimated to be .     

Biodistribution of gold nanoparticles in mouse lung following intratracheal instillation

Background  

The fate of gold nanoparticles, 2, 40 and 100 nm, administered intratracheally to adult female mice was examined. The nanoparticles were traced by autometallography (AMG) at both ultrastructural and light microscopic levels. Also, the gold content was quantified by inductively coupled plasma mass spectrometry (ICP-MS) and neutron activation analysis (NAA). The liver is the major site of deposition of circulating gold nanoparticles. Therefore the degree of translocation was determined by the hepatic deposition of gold. Mice were instilled with 5 intratracheal doses of gold nanoparticles distributed over a period of 3 weeks and were killed 24 h after the last dose. One group of mice were given a single intratracheal dose and were killed after 1 h.     

Pressure dependence of the Fulde-Ferrell-Larkin-Ovchinnikov state in CeCoIn5

Pressure studies of the thermodynamics of CeCoIn5 under magnetic fields H parallel to c and H parallel to ab have been made up to P = 1.34 GPa. We recorded the signature of the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state for all pressures when H parallel to ab. Also remarkably, the FFLO regime suddenly expands for P = 1.34 GPa. With the help of a microscopic theory for d-wave superconductivity, we have extracted the gyromagnetic ratio g and the Fermi velocities nu(a) and nu(c). Our study is the first evidence for the existence of the FFLO state away from the influence of the antiferromagnetic fluctuations. We find a close parallel between the T-P phase diagram of CeCoIn5 and the T-x phase diagram of the high-Tc cuprates, where x is the hole concentration.     

Tuning the pressure-induced superconducting phase in doped CeRhIn5

Pressure- and temperature-dependent heat capacity and electrical resistivity experiments on Sn- and La-doped CeRhIn5 are reported for two samples with specific concentrations, Ce(0.90)La(0.10)RhIn5 and CeRhIn(4.84)Sn(0.16), which present the same TN=2.8 K. The obtained P-T phase diagrams for doped CeRhIn5 compared to that for the pure compound show that Sn doping shifts the diagram to lower pressures while La doping does exactly the opposite, indicating that the important energy scale to define the pressure range for superconductivity in CeRhIn5 is the strength of the on-site Kondo coupling.     

Precursor State to Unconventional Superconductivity in CeIrIn5

We present Hall effect and magnetoresistance measurements in the heavy fermion superconductor CeIrIn(5). At low temperature, a Kondo coherent state is established. Deviations from Kohler's rule and a quadratic temperature dependence of the cotangent of the Hall angle are reminiscent of properties observed in the high-temperature superconducting cuprates. A striking observation pertains to the presence of a precursor state--characterized by a change in the Hall mobility--that precedes the superconductivity in this material, in similarity to the pseudogap in the cuprate superconductors.     

Direct and Indirect Determination of the Magnetocaloric Effect in the Heusler Compound Ni1.7Pt0.3MnGa

Magnetic shape-memory materials are potential magnetic refrigerants, due the caloric properties of their magnetic-field-induced martensitic transformation. The first-order nature of the martensitic transition may be the origin of hysteresis effects that can hinder practical applications. Moreover, the presence of latent heat in these transitions requires direct methods to measure the entropy and to correctly analyze the magnetocaloric effect. Here, we investigated the magnetocaloric effect in the Heusler material Ni1.7Pt0.3MnGa by combining an indirect approach to determine the entropy change from isofield magnetization curves and direct heat-flow measurements using a Peltier calorimeter. Our results demonstrate that the magnetic entropy change ΔS in the vicinity of the first-order martensitic phase transition depends on the measuring method and is directly connected with the temperature and field history of the experimental processes.     

Spectroscopic identification of some derivatives of 3,4-diamino-4H-1,2,4-triazole and 3-Hydrazino-4H-1,2,4-triazole

Spectroscopic methods (ir, ¹H- and ¹³C-nmr, ms and uv) have been used for the structural elucidation and identification of different isomeric 1,2,4-triazole derivatives, obtained by cyclisation reactions from appropriate diaminoguanidines. The four compounds 3,4-diamino-4H-1,2,4-triazole, 3-hydrazino-4H-1,2,4-triazole, 3-amino-4-(2,6-dichlorobenzylideneamino)-4H-1,2,4-triazole and 3-(2,6-dichlorobenzylidenehydrazino)-4H-1,2,4-triazole, were chosen as representative structures to illustrate the general spectroscopic properties for 3,4-diamino- and 3-hydrazino-substituted 4H-1,2,4-triazoles and the corresponding hydrazones, with different substituents in the 5-position of the triazole ring (alkyl-, aralkyl-, mercapto-, hydroxy- and amino-groups). Nmr and uv spectroscopy were found to be the best methods for confirmation of the different series of hydrazones, while ir and nmr were found to be suitable for the structural elucidation of compounds in the series of 3,4-diamino- and 3-hydrazino-4H-1,2,4-triazoles, respectively.     

Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

A highly efficient and stereoselective arylation of in situ-generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition-metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysis.