Novel stereocontrolled addition of allylmetal reagents to alpha-imino esters: efficient synthesis of chiral tetrahydroquinoline derivatives

To prepare in multigram scale new antagonists of the glycine binding site associated to the NMDA receptor, an efficient distereoselective route was set up. The addition of suitable allyltin reagents to chiral N-aryl alpha-imino esters (R-(+)-tert-butyl lactate used as chiral auxiliary), gave the corresponding alpha amino acid-type derivative in high chemical yield and optical purity. This allylation reaction represents a novel example of efficient long-range stereodifferentiation process. In the last part of the synthesis, a regioselective Heck-type cyclization reaction enabled preparation of the target tetrasubstituted exocycle and trisubtituted endocycle double bond derivatives.     

Girard-P derivative of 2-pyridinecarboxaldehyde as analytical reagent. Spectrophotometric determination of copper

The synthesis, characteristics, properties, and reactions with metallic ions of pycolinaldehyde derivatives of Girard-P reagent have been studied. The reagents form complexes with Cu(II), Ni(II), Co(II), Hg(II) and (I), Zn(II), Cd(II), and Fe(III), and (II), which exhibit a good sensibility but whose spectra have the absorption maxima located in the ultraviolet zone. The spectrum of copper complex in the presence of ascorbic acid shows another absorption band at the visible region and this makes the spectrophotometric determination of copper very selective. The influence of the different experimental parameters on the formation of copper complex without ascorbic acid and with this compound was studied, and the optimum conditions for the determination of copper were established. The precision of the procedure, expressed in terms of relative standard deviation, was 1.1%. The method has been tested on “white metal E-8” samples.     

Measurement of the generalized polarizabilities of the proton in virtual Compton scattering at Q2=0.92 and 1.76 GeV2

We report a virtual Compton scattering study of the proton at low c.m. energies. We have determined the structure functions P(LL)-P(TT)/epsilon and P(LT), and the electric and magnetic generalized polarizabilities (GPs) alpha(E)(Q2) and beta(M)(Q2) at momentum transfer Q(2)=0.92 and 1.76 GeV2. The electric GP shows a strong falloff with Q2, and its global behavior does not follow a simple dipole form. The magnetic GP shows a rise and then a falloff; this can be interpreted as the dominance of a long-distance diamagnetic pion cloud at low Q2, compensated at higher Q2 by a paramagnetic contribution from piN intermediate states.     

Enhanced fusion-evaporation cross sections in neutron-rich 132Sn on 64Ni

Evaporation residue cross sections have been measured with neutron-rich radioactive 132Sn beams on 64Ni in the vicinity of the Coulomb barrier. The average beam intensity was 2 x 10(4) particles per second and the smallest cross section measured was less than 5 mb. Large sub-barrier fusion enhancement was observed. Coupled-channel calculations taking into account inelastic excitation significantly underpredict the measured cross sections below the barrier. The presence of several neutron transfer channels with large positive Q values suggests that multinucleon transfer may play an important role in enhancing the fusion of 132Sn and 64Ni.     

Complexation behavior of a highly preorganized 7,7-diphenylnorbornane-derived macrocycle: towards the design of molecular clocks

The syntheses of two new cyclophane hosts, 4 and 6, are described. The main difference between them is the higher degree of preorganization of 4 as a consequence of the inclusion of the 7,7-diphenylnorbornane (DPN) subunit. The inner cavity of 4 adopts a belt-shaped structure, while 6 has a twisted geometry. In the solid state, the molecules of macrocycle 6 are stacked along an axis to form nanotubular structures. Compounds 4 and 6 form two of the strongest complexes between arene cyclophanes and Ag(+) reported up to date. The silver cation is located inside the cavity of the macrocycles. The stability of 4.Ag(+) is considerably higher than that of 6.Ag(+). The additional stabilization of 4.Ag(+) is attributed to higher preorganization of macrocycle 4. DNMR experiments as well as theoretical calculations carried out with 4.Ag(+) show evidence of Ag(+)-hopping between two different binding sites inside the macrocycle. This phenomenon could be the basis for the design of molecular clocks.     

The reproducible properties of correct forecasts

Each period, one outcome out of finitely many possibilities is observed. Each period, a forecaster announces some probability for the future outcomes based on the available data. An outsider wants to know if the forecaster has some knowledge of the data generating process. Let a test be an arbitrary function from sequences of forecasts and outcomes to {0,1}. When the test returns a 0 the test is said to reject the forecasts based on the outcome sequence. When the test resturns a 1 the test is said to not reject the forecasts based on the outcome sequence. Consider any test that does not reject the truth, i.e. it does not reject when the announced forecasts are the conditional probabilities of the data generating process. Based on Fans (1953) Minimax theorem, I show that it is possible to produce forecasts that will not be rejected on any sequence of outcomes. Journal of Economic Literature Classification Number:D83 LearningI thankfully acknowledge financial support from the National Science Foundation grant SES 0109650. I also thank a referee for useful comments. All errors are mine.     

Zeroes of complete polynomial vector fields

We prove that a complete polynomial vector field on has at most one zero, and analyze the possible cases of those with exactly one which is not of Poincaré-Dulac type. We also obtain the possible nonzero first jet singularities of the foliation at infinity and the nongenericity of completeness. Connections with the Jacobian Conjecture are established.

     

Transverse asymmetry AT' from the quasielastic 3He(e,e') process and the neutron magnetic form factor

We have measured the transverse asymmetry A(T') in 3He(e,e(')) quasielastic scattering in Hall A at Jefferson Laboratory with high precision for Q2 values from 0.1 to 0.6 (GeV/c)(2). The neutron magnetic form factor G(n)(M) was extracted based on Faddeev calculations for Q2 = 0.1 and 0.2 (GeV/c)(2) with an experimental uncertainty of less than 2%.     

Novel microscopic mechanism of intermixing during growth on soft metallic substrates

Generic computer simulations using empiric interatomic potentials suggest a new, collective mechanism that could be responsible for mixing at heteroepitaxial interfaces. Even if single adsorbate atoms diffuse by hopping on the substrate surface and do not mix at the terraces, two-dimensional islands formed by nucleation may become unstable above a certain critical size and explode upwards forming clusters of several atomic layers. This process is accompanied by strong distortions of the underlying atomic layers, and on soft materials it can result in surface etching and incorporation of substrate atoms into the islands.