Stereoselective Synthesis and Retentive Trapping of α‐Chiral Secondary Alkyllithiums Leading to Stereodefined α,β‐Dimethyl Carboxylic Esters

The treatment of α‐chiral secondary alkyl iodides with tBuLi at ?100 °C leads to the corresponding secondary alkyllithiums with high retention of configuration. Subsequent quenching with various electrophiles such as Bu₂S₂, DMF, MeOB(OR)₂, or Et₂CO provides the desired products with retention of configuration. Furthermore, a transmetalation with CuBr?P(OEt)₃ also allows retentive trapping with acid chlorides and ethylene oxide. The quenching of the resulting alkyllithiums with ClCO₂Et furnishes stereoselectively syn‐ and anti‐ethyl‐2,3‐dimethyl ester carboxylates (d.r.>94 %). Related esters bearing three adjacent stereo‐controlled centers (stereotriads) have also been prepared. This method has been applied to the synthesis of the ant pheromone (±)‐lasiol in 26 % overall yield (four steps) with d.r.=97:3 starting from commercially available cis‐2,3‐epoxybutane.     

Efficient unbiased variance reduction techniques for Monte Carlo simulations of radiative transfer in cloudy atmospheres: The solution

We present five new variance reduction techniques applicable to Monte Carlo simulations of radiative transfer in the atmosphere: detector directional importance sampling, n-tuple local estimate, prediction-based splitting and Russian roulette, and circum-solar virtual importance sampling. With this set of methods it is possible to simulate remote sensing instruments accurately and quickly. In contrast to all other known techniques used to accelerate Monte Carlo simulations in cloudy atmospheres - except for two methods limited to narrow angle lidars - the presented methods do not make any approximations, and hence do not bias the result. Nevertheless, these methods converge as quickly as any of the biasing acceleration techniques, and the probability distribution of the simulation results is almost perfectly normal. The presented variance reduction techniques have been implemented into the Monte Carlo code MYSTIC (“Monte Carlo code for the physically correct tracing of photons in cloudy atmospheres”) in order to validate the techniques.     

Photo- and electroluminescence of Eu(III) and Tb(III) coordination compounds in thin polyvinylcarbazole films

Organic thin-film structures based on Eu(III), Tb(III), and polyvinylcarbazole coordination compounds are synthesized. Their photo- and electroluminescent properties and volt-ampere and volt-brightness characteristics are investigated.     

Gas-phase halonium metathesis and its competitors. Skeletal rearrangements of cationic adducts of saturated ketones

The methyl cation and CF(3)(+) attack saturated, acyclic ketones to make vibrationally excited adduct ions. Despite their high internal energies and short lifetimes, these adducts undergo deep-seated rearrangements that parallel slower processes in solution. Observed pathways include alkene and alkane expulsions, in addition to (in the case of CF(3)(+)) the precedented loss of CF(2)O + HF. For the vast majority of ketones, the principal charged products are the CF(3)(+) adducts of lighter carbonyl compounds, ions that are not easily prepared by other avenues. Evidence for ion structures comes from collisionally activated unimolecular decomposition and bimolecular ion-molecule reactions. Typical examples are di-n-propyl and diisopropyl ketones (both of which produce CH(3)CH=OCF(3)(+) as the principal ion-molecule reaction product) and pentamethylacetone (which produces (CH(3))(2)C=OCF(3)(+) as virtually the sole ion-molecule reaction product). Isotopic labeling experiments account for mechanisms, and DFT calculations provide a qualitative explanation for the relative abundances of products from unimolecular decompositions of the chemically activated CF(3)(+) adduct ions that are initially formed.     

Bis- and tetrakis(organosilyl) decatungstosilicate,

The high propensity of organosilanes towards polycondensation and reaction with nucleophilic moieties has facilitated the formation of new organic-inorganic hybrids based on the lacunary divacant heteropolyanion [gamma-SiW10O36]8-. Depending on the experimental conditions two different types of derivatives were obtained with the general formula [gamma-SiW10O36(RSi)2O]4- (1) (>90% yield) and [gamma-SiW10O36(RSiO)4]4- (2) (>85% yield) (R = H (1a, 2a), vinyl (1b), -C3H6OC(O)C-(Me)=CH2 (1c, 2c), phenyl (1d, 2d)). The structures of the hybrid anions have been inferred from spectroscopic data, in particular from multinuclear (29Si and 183W) NMR solution studies and from MALDI-TOF mass spectrometry. Both species correspond to the grafting of an oxo-bridged siloxane unit onto the surface of the lacunary polyoxoanion.     

The structure of higher order C60-fullerene-γ-cyclodextrin complexes

C₆₀ inclusion complexes in γ-cyclodextrin are studied by molecular mechanics and semi-empirical methods with the aim of comparing measured and calculated induced circular dichroism (ICD) spectra. Low energy geometries of the complexes are generated by Monte Carlo simulations, also accounting for solvation effects by an aqueous environment. The ICD spectrum of the complex is then obtained from an exciton model based on semi-empirical calculations of the transition energies and the corresponding transition moments. Highly symmetric, tightly bound complexes of two γ-cyclodextrins and buckminsterfullerene are found as the most probable structures. The main bands of the experimentally derived ICD spectrum are assigned to the excitation transitions of the chromophore and are discussed in comparison to calculations on the magnetic circular dichroism (MCD) spectrum of C₆₀.