Oxydation von Allylalkoholen mit Blei(IV)-acetat

Lead tetraacetate (LTA) oxidation of the allylic alcohols 1, 10, 14 and 19 leads to the formation of the epoxides 2, 11, 15 and 20 , products of a novel internal addition reaction of the electron deficient alcohol oxygen to the allylic double bond. In some cases ( 10, 14 ) the formation of a new type of acetoxylated enolethers ( 12, 16 ) is observed. The LTA oxidation of the allylic dienols 21 and 29 gives rise to the formation of the epoxyacetates 25 and 33 , products of a similar internal addition reaction. Furthermore, a variety of cyclization products ( 22, 23, 24, 26, 30, 31, 32 and 34 ) has been isolated whose formation requires an isomerisation of the allylic trans double bond to a cis one.     

Toward a total synthesis of peloruside A: enantioselective preparation of the C8-C19 region

An efficient synthetic sequence toward the C8-C19 region of peloruside A has been developed. The route is highlighted by a selective electrophilic cyclization reaction, a single-step epoxide ring-opening/methylation sequence, and a stereoselective Mukaiyama aldol reaction. [reaction: see text]     

Synthesis of 2,3,4,5-tetranitropyrrole

Dealkylation of 1-tert-butyl-2,3,4-trinitropyrrole in boiling trifluroacetic acid gave 2,3,4-trinitropyrrole, the structure of which was confirmed by X-ray crystallography. Treatment of this trinitropyrrole with nitric acid/oleum briefly at 60° gave 2,3,4,5-tetranitropyrrole.     

The effect of crown ethers on the alkylation of a cyclic β-keto ester

The effects of crown ethers (6 and 7) on the reactions of sodium (2a) and potassium enolates (2b) of 2-ethoxycarbonylcyclohexanone (1) with isopropyl iodide in dimethylsulfoxide and dimethoxyethane have been investigated. When the addition of crown ether promoted dissociation of ion pair 2 in either of the two solvents, the total rate of reaction (k_t) increased and the ratio of carbon- (3) to oxygen-alkylation (4 and 5) products decreased. The results are consistent with the involvement of both the ion pair and more dissociated species in alkylation and with greater reactivity for the latter.     

Engineering switches, genetically

Ostermeier, Guntas, and Mitchel describe a new approach to design enzymes that are allosterically regulated by an unrelated ligand . The resulting protein, constructed by nonhomologous recombination and genetic screens, displays switch-like behavior.     

Spectroscopy of excited state positronium

Electric dipole transitions in the microwave range have been induced between the fine-structure levels of positronium in the excited staten=2. As an indication of the transitions, we used the increase in Lyman- radiation when the metastable 2³S₁-level is depopulated. The results for the transitions 2³S₁2³P_0,1,2 are ₀=18499.65±1.20±4.00 MHz, ₁=13012.42 ±0.65±1.54 MHz and ₂=8624.38±0.54±1.40 MHz. The first error is statistical and the second systematic. The precision of the present measurement has improved by a factor of 3, compared to previous data. Recent bound state QED-calculations have been extended to the orderR _t8 ⁴ln ^–1. The not yet completely calculated orderR _t8 ⁴ is estimated to contribute less than 1 MHz. Our experimental results are in good agreement with theory. By applying a weak magnetic field, we were able to observe the transition 2³S₁2¹P₁ which is strictly forbidden byC-invariance in zero field. Our result, corrected for Zeeman- and motional Starkeffect, is ₃=11180.0±5.0±4.0 MHz. An upper limit for theC-violating matrix element of MHz could be deduced. Our experiment used moderated slow positrons from the bremsstrahlung and pair production of a pulsed electron linear accelerator (TEPOS facility at the university of Giessen).     

Classical irreversibility and mapping of the isosceles triangle billiard

Mapping of the two-dimensional isosceles triangle billiard onto the circular one-dimensional motion of two mass points is described. The singular nature of trajectories directly incident on an acute vertex is discussed in the framework of the present mapping. For an obtuse-angled isosceles triangle, dynamical equations in two-particle space applied to an orbit along a hypotenuse incident on the obtuse vertex suggests irreversible behavior at the critical angle =2/3. Thus it is found that the nonsingular motion of a finite smooth-walled disk on this trajectory exhibits irreversibility. A finite spherical smooth-walled particle moving in a uniform right cylinder whose cross section includes this critical vertex angle likewise exhibits irreversibility. Each such example comprises an irreversible orbit for a single-particle Hamiltonian.     

A graph efficiency multiproduct model of corn/livestock farming: Accounting for nitrate pollution

This paper estimates a non-parametric production frontier for a population of 117 corn/livestock farms in the Corn Belt region in 1987, employing a hyperbolic graph efficiency approach. There are 7 outputs, 39 variable inputs, 4 fixed inputs, and one bad input (residual nitrogen). Three graph efficiency models are estimated. A profit maximization model is specified to estimate a production frontier constrained only by the fixed factors. Two other models involving tax constraints are also estimated. One involves a tax directly on nitrogen and the other involves a tax directly on residual nitrogen, making the disposal of residual nitrogen costly. The nitrogen tax constraint is more effective in reducing residual nitrogen loadings and causes a larger reduction in income than the residual tax constraint.     

A “Multiplicative Coboundary” theorem for some sequences of random matrices

Schmidt(¹⁰) showed that if the family of distributions of the partial sums of a strictly stationary random sequence is tight, then that random sequence is a coboundary. Here an analog of that result is proved for some sequences of random matrices, with partial sums replaced by matrix products.