An Approach to seco-Prezizaane Sesquiterpenoids: Enantioselective Total Synthesis of (+)-1S-Minwanenone

A strategy of general applicability toward seco-prezizaane sesquiterpenes, from a chiral, tricyclic synthon, readily available via an enzymatic resolution step from the Diels-Alder adduct of cyclopentadiene and p-benzoquinone, has been devised. Our approach enables harnessing of the stereochemical proclivities of the norbornyl system to install the desired stereochemistry at the key stereogenic centers. Recourse to an interesting stratagem to realign a stereochemical divergence into stereoreconvergence forms the cornerstone of our successful approach. The first total synthesis of (+)-1S-minwanenone, a prototypical member of seco-prezizaane subclass, has been accomplished.

~(133)Sm的(EC+β~+)衰变和~(133)Pr的1.1s同质异能态

通过96 Ru( 4 0 Ca ,ln2p)反应 ,采用氦喷嘴带传输系统和X γ与γ γ符合测量方法 ,首次建议了133Sm的简单的 (EC + β+)衰变纲图 .由于Ru靶中含有98— 10 2 Ru的成分 ,同时产生了133Pr,并首次测定了133Pr的 1 1 / 2 - 同质异能态的寿命为( 1 .1± 0 .2 )s.用单粒子模型提取了131,133,135 ,137Pr的 1 1 / 2 - 同质异能态的约化跃迁几率的实验值 ,并与Weisscopf近似估计进行了比较 .

Radiative electron capture and subsequent radiative decay in collisions of U89+ ions with N-2

To evaluate the radiative electron capture for the collisions of U89+ ion with N-2, radiative recombination cross sections and the corresponding emitted photon energies are calculated from the ground state 1s(2)2s to 1s(2)2snl(j) (2 <= n <= 9, 0 <= l <= 6) using the newly developed relativistic radiative recombination program RERR06 based on the multiconfiguration Dirac-Fock method. The x-ray spectra for radiative electron capture in the collision have been obtained by convolving the radiative recombination cross sections and the Compton profile of N2. Good agreement is found between the calculated and experimental spectra. In addition, the transition energy levels and probabilities among the 147 levels from the captured 1s(2)2snl(j) have been calculated. From the calculated results, radiative decay cascade processes followed by the radiative electron capture have also been studied with the help of multistep model and coupled rate equations, respectively. The present results not only make us understand the details of the radiative electron captures and the radiative decay cascade spectra in the experiment but also show a more efficient way to obtain the cascade spectra. Finally, the equivalence between the multistep model and coupled rate equations has been shown under a proper condition and the latter can hopefully be extended to investigate other cascade processes.

Photoionization of 1s electron and corresponding shake-up process in ground and excited lithium atoms

The cross sections of the 18 electron photoionization and corresponding shake-up processes for Li atoms in the ground state 1s(2)2s and excited states 1s(2)2p, 1s(2)3p, 1s(2)3p and 1s(2)3d are calculated using the multi-configuration Dirac-Fock method. The latest experimental photoelectron spectrum at hv = 100 eV [Cubaynes D et al. Phys. Rev. Lett. 99 (2007) 213004] has been reproduced by the present theoretical investigation excellently. The relative intensity of the shake-up satellites shows that the effects of correlation and relaxation become more important for the higher excited states of the lithium atom, which are explained very well by the spatial overlap of the initial and final state wavefunctions. In addition, strong dependence of the cross section on the atomic orbitals of the valence electrons are found, especially near the threshold.

gamma cross section in p plus p collisions at root s=200 GeV

We report on a measurement of the gamma(1S + 2S + 3S) -> e(+)e(-) cross section at midrapidity in p + p collisions at root s = 200 GeV. We find the cross section to be 114 +/- 38(stat + fit)(-24)(+23)(syst) pb. Perturbative QCD calculations at next-to-leading order in the color evaporation model are in agreement with our measurement, while calculations in the color singlet model underestimate it by 2 sigma. Our result is consistent with the trend seen in world data as a function of the center-of-mass energy of the collision and extends the availability of gamma data to RHIC energies. The dielectron continuum in the invariant-mass range near the gamma is also studied to obtain a combined yield of e(+)e(-) pairs from the sum of the Drell-Yan process and b-(b) over bar production.

Two Electron Transfer and Stabilization in Slow O6+ and Rare-Gas Collisions

The stabilization ratios.. for double-electron transfer, i.e., the cross section ratios of true double capture to total double-electron transfer, are measured in O6++ He, Ne and Ar collisions at 6 keV/u. A high.. value about 68% is obtained for the He target, while for the Ar target, the.. value is only 8%. The high R value for the He target is due to the significant direct population of the (2l, nl') configurations with high n For the Ar target, the (quasi) symmetric configurations (3l, nl') lead to the much lower.. value. Neglecting the core effects, the O6+ ion can be taken as a bare ion C6+ except the occupied 1s shell, and then the measured R values are compared with previous experimental results of C6+ projectile ions at similar impact velocity. It yields good agreement with the Ne and Ar target, while the occupied 1s shell for the O6++ He system results in a higher R value than that in C6++He collisions.

Positronium-atom collisions

New results are presented for Ps(1s) scattering by H(1s), He(1(1)S) and Li(2s). Calculations have been performed in a coupled state framework, usually employing pseudostates, and allowing for excitation of both the Ps and the atom. In the Ps(1s)-H(1s) calculations the H- formation channel has also been included using a highly accurate H- wave function. Resonances resulting from unstable states in which the positron orbits H- have been calculated and analysed. The new Ps(1s)-He(1(1)S) calculations still fail to resolve existing discrepancies between theory and experiment at very low energies. The possible importance of the Ps(-) formation channel in all three collision systems is discussed. (C) 2004 Elsevier B.V. All rights reserved.

Electron spectroscopy of doubly excited states in He produced by slow collisions of He2+ ions with Ba atoms

We measured ejected electron spectra caused by autoionization of doubly excited states in He atoms; the excited He was made by double electron capture of low-energy He2+ ions colliding with Ba atoms. Measurements were performed by means of zero degree electron spectroscopy at projectile energies from 40 to 20 keV. Electron spectra due to autoionization from the states He(2lnl') to He+(1s) for n greater than or equal to2, and those from He(3lnl') to He+ (2s or 2p) for n greater than or equal to3, were observed. Line peaks in the spectra were identified by comparing observed electron spectra with those of several theoretical calculations. It was found that doubly excited states of relatively high angular momenta such as the D and F terms were conspicuously created in a quite different manner from the cases of the production of doubly excited states by the use of photon, electron, or ion impacts on neutral He atoms. Rydberg states with large n values were observed with high population in both the He(2lnl') and He(3lnl') series. Other remarkable features in the electron spectra are described and the mechanisms for the production of these electron spectra are discussed qualitatively.

Charge exchange and dissociative processes in collisions of slow He2+ ions with H2O molecules

Experimental and theoretical studies of one-electron capture in collisions of He2+ ions with H2O molecules have been carried out in the range 0.025-12 keV amu(-1) corresponding to typical solar wind velocities of 70-1523 km s(-1). Translational energy spectroscopy (TES), photon emission spectroscopy (PES), and fragment ion spectroscopy were employed to identify and quantify the collision mechanisms involved. Cross sections for selective single electron capture into n=1, 2, and 3 states of the He+ ion were obtained using TES while PES provided cross sections for capture into the He+(2p) and He+(3p) states. Our model calculations show that He+(n=2) and He+(n=3) formation proceeds via a single-electron process governed by the nucleus-electron interaction. In contrast, the He+(1s) formation mechanism involves an exothermic two-electron process driven by the electron-electron interaction, where the potential energy released by the electron capture is used to remove a second electron thereby resulting in fragmentation of the H2O molecule. This process is found to become increasingly important as the collision energy decreases. The experimental cross sections are found to be in reasonable agreement with cross sections calculated using the Demkov and Landau-Zener models.

Asymmetric synthesis of (1R,2S,3R)-3-methylcispentacin and (1S,2S,3R)-3-methyltranspentacin by kinetic resolution of tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate

Conjugate addition of lithium dibenzylamide to tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate occurs with high levels of stereocontrol, with preferential addition of lithium dibenzylamide to the face of the cyclic alpha,beta-unsaturated acceptor anti- to the 3-methyl substituent. High levels of enantiorecognition are observed between tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate and an excess of lithium (+/-)-N-benzyl-N-alpha-methylbenzylamide (10 eq.) (E > 140) in their mutual kinetic resolution, while the kinetic resolution of tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate with lithium (S)-N-benzyl-N-alpha-methylbenzylamide proceeds to give, at 51% conversion, tert-butyl (1R, 2S, 3R,alphaS)-3-methyl-2-N-benzyl-N-alpha-methylbenzylaminocyclopentane-1-c arboxylate consistent with E > 130, and in 39% yield and 99 +/- 0.5% de after purification. Subsequent deprotection by hydrogenolysis and ester hydrolysis gives (1R, 2S, 3R)-3-methylcispentacin in > 98% de and 98 +/- 1% ee. Selective epimerisation of tert-butyl (1R, 2S, 3R, alphaS)-3-methyl-2-N- benzyl-N-alpha-methylbenzylaminocyclopentane-1-carboxylate by treatment with (KOBu)-Bu-t in (BuOH)-Bu-t gives tert-butyl (1S, 2S, 3R, alphaS)-3-methyl-2-N-benzyl-N-alpha-methylbenzylaminocyclopentane-1-carb oxylate in quantitative yield and in > 98% de, with subsequent deprotection by hydrogenolysis and ester hydrolysis giving (1S, 2S, 3R)-3-methyltranspentacin hydrochloride in > 98% de and 97 +/- 1% ee.