Regioselective Synthesis of Trichloromethyl‐Substituted Salicylates and Cyclohexenones by One‐Pot Cyclizations of 1,3‐Bis(trimethylsilyloxy)buta‐1,3‐dienes

A variety of 6‐(trichloromethyl)salicylates (=2‐hydroxy‐6‐(trichloromethyl)benzoates) were prepared by TiCl₄‐mediated cyclization of 1,3‐bis(trimethylsilyloxy)buta‐1,3‐dienes with 1,1,1‐trichloro‐4,4‐dimethoxybut‐3‐en‐2‐one. The employment of trimethylsilyl trifluoromethanesulfonate (Me₃SiOTf) as Lewis acid resulted in the formation of trichloromethyl‐substituted cyclohexenones. The cyclizations proceeded with good‐to‐very‐good regioselectivities.     

Predicting DAX trends from Dow Jones data by methods of the mathematical theory of democracy

The mathematical theory of democracy operates on the indices of popularity and universality which are used to find socially optimal representatives and representative bodies. Regarded mathematically, neither the ‘society’, nor its ‘representatives’ are necessarily human, so that some objects can represent the behavior of other objects. This idea is applied to predicting the DAX-trends (German stock index) from the actual Dow-Jones data; the current fluctuations of stock prices in New York are regarded as representative indicators of future stock price fluctuations in Frankfurt. In particular, it is found that American Express anticipates on the average the price ±fluctuations of 2/3 of the DAX stocks. The statistical significance of the null hypothesis that such a bias from the uncertainty 50% can occur by chance is only 3.5%.     

Evaluation of German parties and coalitions by methods of the mathematical theory of democracy

The paper continues author’s studies on applications of the mathematical theory of democracy. Five German leading parties and their coalitions are evaluated with indices of popularity and universality to show how well they represent the electorate. The evaluation goes beyond the information on election results and uses an operational representation of party manifestos.     

Assessment of density functional methods for reaction energetics: Iridium‐catalyzed water oxidation as case study

We investigate basis set convergence for a series of density functional theory (DFT) functionals (both hybrid and nonhybrid) and compare to coupled‐cluster with single and double excitations and perturbative triples [CCSD(T)] benchmark calculations. The case studied is the energetics of the water oxidation reaction by an iridium‐oxo complex. Complexation energies for the reactants and products complexes as well as the transition state (TS) energy are considered. Contrary to the expectation of relatively weak basis set dependence for DFT, the basis set effects are large, for example, more than 10 kcal mol^?1 difference from converged basis for the activation energy with “small” basis sets (DZ/6‐31G** for Ir/other atoms, or SVP) and still more than 6 kcal mol^?1 for def2‐TZVPP/6‐31G**. Inclusion of the dispersion correction in DFT‐D3 schemes affects the energies of reactant complex (RC), TS, and product complex (PC) by almost the same amount; it significantly improves the complexation energy (the formation of RC), but has little effect on the activation energy with respect to RC. With converged basis, some pure GGAs (PBE‐D3, BP86‐D3) as well as the hybrid functional B3LYP‐D3 are very accurate compared to benchmark CCSD(T) calculations. © 2012 Wiley Periodicals, Inc.     

Selecting predictors for traffic control by methods of the mathematical theory of democracy

The mathematical theory of democracy operates on the indices of popularity and universality which are used to find socially optimal representatives and representative bodies. Regarded mathematically, neither the ‘society’, nor its ‘representatives’ are necessarily human, so that some objects can represent the behavior of other objects. This idea is applied to selecting predictors of traffic jams which occur the City Ring of Hagen, Germany; the traffic situations at street intersections all over the town are regarded as representatives of future traffic situations at the Ring intersections. As a result, a reliable prediction can be attained by already five surveillance cameras installed at appropriate locations. The selection of such locations and processing the data captured by the cameras constitute the subjects of this paper.     

Pyrimidopteridine-catalyzed Photo-mediated Hydroacetoxylation

Herein we report a photo-mediated formal addition of carboxylic acids to activated alkenes catalyzed by a pyrimidopteridine photoredox catalyst. The decarboxylation of aliphatic carboxylic acids upon single-electron oxidation is countered in the presence of electron-rich alkenes and a hydroacetoxylation is observed. Mechanistic proposals have been made based on CV measurements, competitive Stern-Volmer quenching and EPR experiments. Evidence that tetra-N-substituted pyrimidopteridines function as dual photoredox and hydrogen atom transfer catalyst was supported by spectroscopic means.     

Pyrimidopteridine N-Oxide Organic Photoredox Catalysts: Characterization,Application and Non-Covalent Interaction in Solid State

Herein we report the photo- and electrochemical characterization of pyrimidopteridine N-oxide-based heterocycles. The potential of their application as organic photoredox catalysts is showcased in the photomediated contra-thermodynamic E→Z isomerization of cinnamic acid derivatives and oxidative cyclization of 2-phenyl benzoic acid to benzocoumarin using molecular oxygen as a mild oxidant. Furthermore, unprecedented intermolecular non-covalent n–π-hole interactions in solid state are discussed based on crystallographic and theoretical data.     

Analysis of the third European survey on working conditions with composite indicators

A composite indicator Working conditions for comparing European countries is constructed from data of the Third European Survey on Working Conditions. The main findings are as follows: (a) European countries differ with respect to working conditions statistically more significantly than with respect to earnings; it implies a quite accurate discrimination threshold in ranking countries with respect to working conditions, (b) working conditions and earnings positively correlate over the whole of Europe but correlate little within single countries; it indicates at the prevailing role of national determinants over professional or social specificities as contributing to the average working conditions, and (c) earnings play no essential role in subjective estimations, including job satisfaction, which mainly depends on working conditions; consequently, more attention should be paid to improving the latter.     

Synthesis of fluorinated purine and 1-deazapurine glycosides as potential inhibitors of adenosine deaminase

The synthesis of 2- and 6-trifluoromethylated purines and 1-deazapurines was performed by formal [3 + 3]-cyclization reactions of 5-aminoimidazoles with a set of trifluoromethyl-substituted 1,3-CCC- and 1,3-CNC-dielectrophiles. The corresponding fluorinated nucleosides were synthesized by glycosylation of 9-unsubstituted purines and 1-deazapurines with peracetylated β-ribose, β-glucose, and rhamnose and subsequent deprotection. These scaffolds can be considered as potential inhibitors of adenosine deaminase (ADA) and inosine monophosphate dehydrogenase (IMPDH) enzymes.