A modular design of ruthenium(II) catalysts with chiral C2-symmetric phosphinite ligands for effective asymmetric transfer hydrogenation of aromatic ketones

Hydrogen-transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity. The new chiral C₂-symmetric ligands N,N′-bis-[(1S)-1-sec-butyl-2-O-(diphenylphosphinite)ethyl]ethanediamide, 1 and N,N′-bis-[(1S)-1-phenyl-2-O-(diphenylphosphinite)ethyl]ethanediamide, 2 and the corresponding ruthenium complexes 3 and 4 have been prepared and their structures have been elucidated by a combination of multi-nuclear NMR spectroscopy, IR spectroscopy, and elemental analysis. ¹H–³¹P NMR, DEPT, ¹H–¹³C HETCOR, or ¹H–¹H COSY correlation experiments were used to confirm the spectral assignments. The catalytic activity of complexes 3 and 4 in transfer hydrogenation of acetophenone derivatives by iso-PrOH has also been studied. Under optimized conditions, these chiral ruthenium complexes serve as catalyst precursors for the asymmetric transfer hydrogenation of acetophenone derivatives in iso-PrOH and act as excellent catalysts, giving the corresponding chiral alcohols in 99% yield and up to 75% ee. This transfer hydrogenation is characterized by low reversibility under these conditions.     

FRACTOP: A Geometric Partitioning Metaheuristic for Global Optimization

We propose a new metaheuristic, FRACTOP, for global optimization. FRACTOP is based on the geometric partitioning of the feasible region so that search metaheuristics such as Simulated Annealing (SA), or Genetic Algorithms (GA) which are activated in smaller subregions, have increased reliability in locating the global optimum. FRACTOP is able to incorporate any search heuristic devised for global optimization. The main contribution of FRACTOP is that it provides an intelligent guidance (through fuzzy measures) in locating the subregion containing the global optimum solution for the search heuristics imbedded in it. By executing the search in nonoverlapping subregions, FRACTOP eliminates the repetitive visits of the search heuristics to the same local area and furthermore, it becomes amenable for parallel processing. As FRACTOP conducts the search deeper into smaller subregions, many unpromising subregions are discarded from the feasible region. Thus, the initial feasible region gains a fractal structure with many space gaps which economizes on computation time. Computational experiments with FRACTOP indicate that the metaheuristic improves significantly the results obtained by random search (RS), SA and GA.     

On the effective field and optical constants of alkali halides containingF colour centres

Summary The Onsager and Lorentz local fields ofF colour centres are compared and their change as a function of angular frequency and temperature is also considered. The change of these fields is proportional to the change of the refractive index produced byF centres. Some approximations about the explicit temperature dependence of the refractive-index change are also presented.

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Riassunto I campi locali di Onsager e Lorentz diF centri di colore sono confrontati e si considera il loro cambiamento in funzione della frequenza angolare e della temperatura. Il cambiamento di questi campi è proporzionale al cambiamento dell'indice di rifrazione prodotto daF centri. Si presentano anche alcune approssimazioni riguardo alla esplicita dipendenza dalla temperatura del cambiamento dell'indice di rifrazione.

     

Characteristic classes of flat bundles, II

On a smooth varietyX defined over a fieldK of characteristic zero, one defines characteristic classes of bundles with an integrableK-connection in a group lifting the Chow group, which map, whenK is the field of complex numbers andX is proper, to Cheeger-Simons' secondary analytic invariants, compatibly with the cycle map in the Deligne cohomology.